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show that ln(x) =< x-1 ??
A
anzerftum
how do i show that ln(x) is less or equal to x-1?
we can assume that e^x is larger or equal to x+1.
it doesn't say we can assume anything else (ie, inverse of e is ln, algebra of logs etc..)
that's why i'm stuggling to prove this without extra assumptions
Reply 1
A
anzerftum
OP
sorry, bad notation. we can assume that e^y is larger or equal to y+1.
Reply 2
A
mmmpie
12
It doesn't mean you can't use . It's not an assumption.
Reply 3
A
qgujxj39
17
We can definitely assume that exp and ln are inverses, this is basically the definition of ln.
Reply 4
A
Iron&Wine
Original post
by anzerftum
how do i show that ln(x) is less or equal to x-1?
we can assume that e^x is larger or equal to x+1.
it doesn't say we can assume anything else (ie, inverse of e is ln, algebra of logs etc..)
that's why i'm stuggling to prove this without extra assumptions
Reply 5
A
anzerftum
OP
Original post
by mmmpie
It doesn't mean you can't use . It's not an assumption.
so just plug in x=e^y? simple as?
Reply 6
A
anzerftum
OP
Original post
by mmmpie
It doesn't mean you can't use . It's not an assumption.
to get e^x>x+1 which we're assuming true?
Reply 7
A
qgujxj39
17
Original post
by anzerftum
so just plug in x=e^y? simple as?
Pretty much, although we need to be careful, you're probably going to have to use the fact that it's an increasing function, so the inequality is preserved.
Reply 8
A
Zuzuzu
12
Given this question on it's own I'd consider ln(x) - x + 1 either side of a certain value.
Given the hint, though, try making a substitution.
Reply 9
A
anzerftum
OP
Original post
by tommm
Pretty much, although we need to be careful, you're probably going to have to use the fact that it's an increasing function, so the inequality is preserved.
so okay, we're using the substitution to show the assumption e^y>y+1 which we're assuming true?
shouldn't we use the assumption to show that ln(x) =< x-1 ? the above seems kind of "inside-out"
Reply 10
A
mmmpie
12
Original post
by anzerftum
Original post
by anzerftum
so just plug in x=e^y? simple as?
Where did you get that from?
You're trying to prove
Unparseable LaTeX formula:
\ln x \leq x-1
, so I'd begin with
Unparseable LaTeX formula:
e^{\ln x} \leq e^{x-1}
EDIT: Oh, right, I see the substitution. Senior moment there.
Reply 11
A
anzerftum
OP
Original post
by mmmpie
Where did you get that from?
You're trying to prove
Unparseable LaTeX formula:
\ln x \leq x-1
, so I'd begin with
Unparseable LaTeX formula:
e^{\ln x} \leq e^{x-1}
EDIT: Oh, right, I see the substitution. Senior moment there.
thank you
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10: Properties and Reactions of Alkenes
Chem 12A: Organic Chemistry Fall 2022
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Mon, 11 Jul 2022 19:10:43 GMT
10.4: Degrees of Unsaturation
391372
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Andy Wells
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Contents
1. Home
2. Campus Bookshelves
3. Chabot College
4. Chem 12A: Organic Chemistry Fall 2022
5. 10: Properties and Reactions of Alkenes
6. 10.4: Degrees of Unsaturation
Expand/collapse global location
Chem 12A: Organic Chemistry Fall 2022
Front Matter
1: Introduction to Organic Chemistry- review of atoms and molecules
2: Polarity, Intermolecular Forces, and Physical Properties of Molecules
3: Representations of Organic Molecules
4: Acids and Bases
5: Alkanes and Conformations
6: Stereoisomerism
7: Introduction to Organic Reactions
8: Nucleophilic Substitution Reactions
9: Elimination Reactions
10: Properties and Reactions of Alkenes
11: Properties and Reactions of Alkynes
12: Free Radical Reactions
13: Properties and Reactions of Alcohols
14: Infrared Spectroscopy and Mass Spectrometry
15: Nuclear Magnetic Resonance Spectroscopy
Back Matter
10.4: Degrees of Unsaturation
Last updated Jul 11, 2022
Save as PDF
10.3: The Alkene Double Bond and Stereoisomerism
10.5: The E/Z System (when cis/trans does not work)
Page ID 391372
( \newcommand{\kernel}{\mathrm{null}\,})
Table of contents
1. Saturated and Unsaturated Molecules
2. Calculating The Degree of Unsaturation (DU)
1. References
Contributors and Attributions
Learning Objectives
calculate the Degrees of Unsaturation (DU) and apply it to alkene structure
Saturated and Unsaturated Molecules
In the lab, saturation may be thought of as the point when a solution cannot dissolve anymore of a substance added to it. In terms of degrees of unsaturation, a molecule only containing single bonds with no rings is considered saturated.
CH 3 CH 2 CH 31-methyoxypentane
Unlike saturated molecules, unsaturated molecules contain double bond(s), triple bond(s) and/or ring(s).
CH 3 CH=CHCH 33-chloro-5-octyne
There are many ways one can go about determining the structure of an unknown organic molecule. Although, nuclear magnetic resonance (NMR) and infrared radiation (IR) are the primary ways of determining molecular structures, these techniques require expensive instrumentation and are not always readily available. Fortunately, calculating the degrees of unsaturation provides useful information about the structure. The degree of unsaturation indicates the total number of pi bonds and rings within a molecule which makes it easier for one to figure out the molecular structure.
DU = Degrees of Unsaturation = (number of pi bonds) + (number of rings)
Alkenes (R 2 C=CR 2) and alkynes (R–C≡C–R) are called unsaturated hydrocarbons because they have fewer hydrogen atoms than does an alkane with the same number of carbon atoms, as is indicated in the following general formulas:
Calculating The Degree of Unsaturation (DU)
If the molecular formula is given, plug in the numbers into this formula:
(7.2.1)DoU=2C+2+N−X−H 2
C is the number of carbons
N is the number of nitrogens
X is the number of halogens (F, Cl, Br, I)
H is the number of hydrogens
The molecular formula of a hydrocarbon provides information about the possible structural types it may represent. A saturated molecule contains only single bonds and no rings. Another way of interpreting this is that a saturated molecule has the maximum number of hydrogen atoms possible to be an acyclic alkane. Thus, the number of hydrogens can be represented by 2C+2, which is the general molecular representation of an alkane. As an example, for the molecular formula C3H4 the number of actual hydrogens needed for the compound to be saturated is 8
[2C+2=(2x3)+2=8.]
The compound needs 4 more hydrogens in order to be fully saturated (expected number of hydrogens-observed number of hydrogens=8-4=4). Degrees of unsaturation is equal to 2, or half the number of hydrogens the molecule needs to be classified as saturated. Hence, the DoB formula divides by 2. The formula subtracts the number of X's because a halogen (X) replaces a hydrogen in a compound. For instance, in chloroethane, C2H5Cl, there is one less hydrogen compared to ethane, C2H6. For example, consider compounds having the formula C5H8. The formula of the five-carbon alkane pentane is C5H12 so the difference in hydrogen content is 4. This difference suggests such compounds may have a triple bond, two double bonds, a ring plus a double bond, or two rings. Some examples are shown here, and there are at least fourteen others!
For a compound to be saturated, there is one more hydrogen in a molecule when nitrogen is present. Therefore, we add the number of nitrogens (N). This can be seen with C 3 H 9 N compared to C 3 H 8. Oxygen and sulfur are not included in the formula because saturation is unaffected by these elements. As seen in alcohols, the same number of hydrogens in ethanol, C 2 H 5 OH, matches the number of hydrogens in ethane, C 2 H 6.
The following chart illustrates the possible combinations of the number of double bond(s), triple bond(s), and/or ring(s) for a given degree of unsaturation. Each row corresponds to a different combination.
One degree of unsaturation is equivalent to 1 ring or 1 double bond (1 π bond).
Two degrees of unsaturation is equivalent to 2 double bonds, 1 ring and 1 double bond, 2 rings, or 1 triple bond (2 π bonds).
When the DU is 4 or greater, the presence of benzene rings is very likely.
| DU | Possible combinations of rings/ bonds |
--- |
| | # of rings | # of double bonds | # of triple bonds |
| 1 | 1 | 0 | 0 |
| | 0 | 1 | 0 |
| 2 | 2 | 0 | 0 |
| | 0 | 2 | 0 |
| | 0 | 0 | 1 |
| | 1 | 1 | 0 |
Remember, the degrees of unsaturation only gives the sum of double bonds, triple bonds and/or rings. For instance, a degree of unsaturation of 3 can contain 3 rings, 2 rings+1 double bond, 1 ring+2 double bonds, 1 ring+1 triple bond, 1 double bond+1 triple bond, or 3 double bonds.
Example: Benzene
What is the Degree of Unsaturation for Benzene?
Solution
The molecular formula for benzene is C 6 H 6. Thus,
DU= 4, where C=6, N=0,X=0, and H=6. 1 DoB can equal 1 ring or 1 double bond. This corresponds to benzene containing 1 ring and 3 double bonds.
However, when given the molecular formula C 6 H 6, benzene is only one of many possible structures (isomers). The following structures all have DU of 4 and have the same molecular formula as benzene. However, these compounds are very rare, unlike benzene. We will learn more about the reasons for benzen's high stability when we studey aromaticity in later chapters.
Exercises
Are the following molecules saturated or unsaturated:
(b.) (c.) (d.) C 10 H 6 N 4
Using the molecules from (1) above, give the degrees of unsaturation for each.
Calculate the degrees of unsaturation, classify the compound as saturated or unsaturated, and list all the ring/pi bond combination possible for the following molecular formulas: (a.) C 9 H 20(b.) C 7 H 8(c.) C 5 H 7 Cl (d.) C 9 H 9 NO 4
Calculate degrees of unsaturation (DoU) for the following, and propose a structure for each.
a) C 5 H 8
b) C 4 H 4
Calculate the degree of unsaturation (DoU) for the following molecules
a) C 5 H 5 N
b) C 5 H 5 NO 2
c) C 5 H 5 Br
The following molecule is caffeine (C 8 H 10 N 4 O 2), determine the degrees of unsaturation (DoU).
Answer
1.
(a.) unsaturated (E ven though rings only contain single bonds, rings are considered unsaturated.)
(b.) unsaturated
(c.) saturated
(d.) unsaturated
If the molecular structure is given, the easiest way to solve is to count the number of double bonds, triple bonds and/or rings. However, you can also determine the molecular formula and solve for the degrees of unsaturation by using the formula.
(a.)2
(b.) 2(one double bond and the double bond from the carbonyl)
(c.) 0
(d.) 10
3.
(a.) DU =0; saturated(Remember-a saturated molecule only contains single bonds)
(b.) DU = 4; unsaturatedThe molecule can contain any of these combinations of rings and pi bonds that add up to 4, such as(i) 4 double bonds (ii) 4 rings (iii) 2 double bonds+2 rings (iv) 1 double bond+3 rings (v) 3 double bonds+1 ring (vi) 1 triple bond+2 rings (vii) 2 triple bonds (viii) 1 triple bond+1 double bond+1 ring (ix) 1 triple bond+2 double bonds
(c.) DU = 2; unsaturated (i) 1 triple bond (ii) 1 ring+1 double bond (iii) 2 rings (iv) 2 double bonds
(d.) DU = 6; (i) 3 triple bonds (ii) 2 triple bonds+2 double bonds (iii) 2 triple bonds+1 double bond+1 ring (iv)...(As you can see, the degrees of unsaturation only gives the sum of double bonds, triple bonds and/or ring. Thus, the formula may give numerous possible structures for a given molecular formula.)
4.
5.a)4 b) 4 c) 3
6.DU =6
References
Vollhardt, K. P.C. & Shore, N. (2007). Organic Chemistry(5 th Ed.). New York: W. H. Freeman. (473-474)
Shore, N. (2007). Study Guide and Solutions Manual for Organic Chemistry(5 th Ed.). New York: W.H. Freeman. (201)
Contributors and Attributions
Dr. Dietmar Kennepohl FCIC (Professor of Chemistry, Athabasca University)
Prof. Steven Farmer (Sonoma State University)
Kim Quach (UCD)
10.4: Degrees of Unsaturation is shared under a not declared license and was authored, remixed, and/or curated by LibreTexts.
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15103 | https://books.google.com/books/about/Heat_Transfer.html?id=GajCQgAACAAJ | Heat Transfer - Jack Philip Holman - Google Books
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Heat Transfer
Jack Philip Holman
McGraw-Hill, 2002 - Science - 665 pages
As one of the most popular heat transfer texts, Jack Holman's HEAT TRANSFER is noted for its clarity, accessible approach, and inclusion of many examples and problem sets. The new Ninth Edition retains the straight-forward, to-the-point writing style while covering both analytical and empirical approaches to the subject. Throughout the book, emphasis is placed on physical understanding while, at the same time, relying on meaningful experimental data in those situations that do not permit a simple analytical solution. New examples and templates provide students with updated resources for computer-numerical solutions.
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Contents
CHAPTER 1 3
CHAPTER 5
Dimensions 73
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Heat Transfer
Jack Philip Holman
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Heat Transfer
Jack Philip Holman
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aluminumanalysisAssumeboundary conditionsboundary layerBtu/hC₁Calculate the heatCalculate the temperaturecondensationconstant heat fluxconvection boundaryconvection coefficientconvection environmentconvection heat transferconvection heat-transfer coefficientcoolingcoppercylinderdiffusiondiskemissivityenergy balanceFigure Exampleflat plateflow ratefluidfree convectionft²heat conductedheat exchangerheat flowheat lossheat-transfer ratehorizontalincrementsinsideinsulationisothermalkg/m³kg/slaminarliquidlostm²/smaintainednodal equationsNusseltobtainone-dimensionaloverall heat-transfer coefficientpipeproblempropertiesradiosityReynolds numbersemi-infiniteshape factorshown in Figuresolidsolutionspherestainless steelsteady-statesuddenly exposedsurface temperatureT₁Tabletemperaturetemperature differencetemperature distributionthermal conductivitythermal radiationthermal resistancethicknesstotal heatTP+1tube wallturbulentunit lengthvelocityverticalW/m²wall temperatureΔτдудх
Bibliographic information
Title Heat Transfer
McGraw-Hill series in mechanical engineering
AuthorJack Philip Holman
Edition 9, illustrated
Publisher McGraw-Hill, 2002
Original from the University of Michigan
Digitized Aug 26, 2011
ISBN 0071122303, 9780071122306
Length 665 pages
SubjectsScience
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Mechanics
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Thermodynamics
Science / Mechanics / Thermodynamics
Technology & Engineering / Mechanical
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15104 | https://arxiv.org/pdf/2009.03412 | Analysis of landscape hierarchy during coarsening and aging in Ising spin glasses
Stefan Boettcher and Mahajabin Rahman
Department of Physics, Emory University, Atlanta, GA 30322, USA
We use record dynamics (RD), a coarse-grained description of the ubiquitous relaxation phe-nomenology known as "aging", as a diagnostic tool to find universal features that distinguish between the energy landscapes of Ising spin models and the ferromagnet. According to RD, a non-equilibrium system after a quench relies on fluctuations that randomly generate a sequence of irreversible record-sized events (quakes or avalanches) that allow the system to escape ever-higher barriers of meta-stable states within a complex, hierarchical energy landscape. Once these record events allow the system to overcome such barriers, the system relaxes by tumbling into the following meta-stable state that is marginally more stable. Within this framework, a clear distinction can be drawn between the coarsening dynamics of an Ising ferromagnet and the aging of the spin glass, which are often put in the same category. To that end, we interpolate between the spin glass and ferromagnet by varying the admixture p of ferromagnetic over anti-ferromagnetic bonds from the glassy state (at 50% each) to wherever clear ferromagnetic behavior emerges. The accumulation of record events grows logarithmic with time in the glassy regime, with a sharp transition at a specific admixture into the ferromagnetic regime where such activations saturate quickly. We show this ef-fect both for the Edwards-Anderson model on a cubic lattice as well as the Sherrington-Kirkpatrick (mean-field) spin glass. While this transition coincides with a previously observed zero-temperature equilibrium transition in the former, that transition has not yet been described for the latter.
I. INTRODUCTION
The morphology of complex energy landscapes [1, 2], and the parameters that control it, are of continuing in-terest in a large variety of scientific endeavors, from pro-tein folding and evolutionary landscapes in biology [3–7], the design of amorphous materials [8–18], to the hard-ness of combinatorial optimization problems [5, 19–23]. The challenges encountered in describing the geometry of the extremely high-dimensional space of attainable con-figurations are enormous [1, 2, 12, 23–28]. The structure of such energy landscapes hugely impacts the dynamics of statistical systems evolving through them. While re-laxation in simple, smooth landscapes is rapid, like the exponential cooling of a cup of coffee , relaxation in complex energy landscapes can possess a myriad of metastable states to temporarily or permanently trap any dynamic process. In turn, simple relaxation processes can serve as diagnostic tools to explore features of land-scapes [19, 24, 25, 27, 30–32]. It is particularly enticing when it is possible to discover universal aspects of such landscapes that allow to categorize those features and, ultimately, predict and control dynamic behavior. Variations in temperature can be used to take a full measure of landscapes. At high temperature correspond-ingly higher echelons in energy get explored, while an-nealing or quenching is used to trace out a descent through the landscape towards configurations of lower en-ergy. A conceptually simple protocol consists of prepar-ing a system at a high temperature, where it equilibrates easily, and then instantaneously quenching it down to a fixed, low temperature, to explore how it relaxes towards equilibrium thereafter. Such an “aging” protocol , when applied to systems in a complex energy landscape, elicits quite subtle relaxation behaviors which, unlike for the coffee mentioned above, keeps the system far from a new equilibrium for very long times. Anomalously slow relaxation and full aging in a complex landscape ensues when downward paths are obstructed by barriers, ener-getic or entropic, that trap the system in neighborhoods with many local minima. The aging phenomenology is associated with memory effects by which the current activity is imprinted by a dependence on the waiting time tw since the quench. For a wide class of systems, generally considered to be glassy, it is found that correlations, instead of being time trans-lational invariant, G(t, t w) ∼ f (t − tw), roughly depend on a ratio, G ∼ f (t/t w). Although memory effects in out-of-equilibrium systems are generally of interest, that fact alone is not sufficient to categorize its energy landscape as complex or glassy. To emphasize this fact, and to pro-vide a deeper insight into the relation between landscape morphology and aging dynamics, we investigate here the aging in families of models that interpolate between a well-known spin glass [34, 35] and the corresponding fer-romagnet . Albeit glass and ferromagnet exhibit sim-ilar scaling with age t, it stands to reason that the aging dynamics of a homogeneous ferromagnet differs signifi-cantly from that of a glass. In contrast to the hierarchi-cal, multimodal energy landscape of a glass [37–41], that of a ferromagnet is smooth. Yet, much of the literature leads to the impression that relaxation via coarsening in a ferromagnet and glassy aging are synonymous [42–44]. Technically, one could argue that the fact that in either extreme a growing length-scale emerges is indicative of coarsening domains. We posit that the process by which those length-scales grow with age, logarithmically in the glassy case and with a power-law for a ferromagnet, is fundamentally different. As discussed in Ref. , energy barriers that scale with the size of a domain to be flipped imply that fur-ther growth in those domains is curtailed to be merely
arXiv:2009.03412v2 [cond-mat.dis-nn] 7 Jan 2021
2logarithmic in time. Such a feedback does not emerge in the coarsening of a ferromagnetic Ising system, where energy barriers remain insensitive to the size of the do-main to be flipped. Accordingly, the landscape of a glassy system has a hierarchical structure in that, the lower an energy it has reached, the higher the barriers get, and thus, the harder it becomes to escape local minima . In a homogeneously coarsening system, energy barriers remain largely independent of the depth reached within the landscape, providing some roughness and metastabil-ity but of bounded scale beyond which the structure is relatively smooth. Within the aging process, this differ-ence manifests itself dramatically in the manner that the relaxing system responds to fluctuations, as illustrated in Fig. 2. In a ferromagnet, average fluctuations in energy, beyond some low, fixed threshold, suffice to cross typ-ical barriers, often followed by disproportionately large expulsions of heat. In contrast, to advance glassy sys-tems with diverging energy barriers, mere average fluc-tuations become ineffective. To be able to relax, those fluctuations have to produce ever new records in their size to overcome ever steeper barriers, which is the basis of what is called Record Dynamics (RD) . Such record-production, decorrelated by a wide separation in time, is known to unfold only on a logarithmic scale [48, 49]. Although irrelevant for the cases studied in Ref. (and here), it should be noted that entropic effects can become dominant and may entail diverging free-energy barriers with domain size, even in an otherwise homoge-nous system. One example is a 3-spin Ising ferromag-net . Systems driven by entropic barriers, such as the free volume in a hard-core colloidal system, are referred to as “structural” glasses. In those systems, a hierarchical free-energy landscape emerges dynamically . In the following, we define a simple coarse-graining pro-cedure, counting the number of “valleys” traversed in the energy landscape, that effectively probes the impact of fluctuations on the aging dynamics. Our focus on land-scape morphology reveals the nature of the irreversible, intermittent events that allow the expulsion of excess en-ergy from the system. It shows a dynamical transition between a glassy and a ferromagnetic relaxation regime based on this measure. In that, we reproduce similar findings using scaling exponents of two-time correlation functions in the thermodynamic limit , which indi-cated that this dynamical transition is closely related with a zero-temperature equilibrium transition between a glass and a ferromagnet . That this transition tran-scends into the non-equilibrium realm highlights the fact that aging in a glassy system is a distinct process from what is found in homogeneous systems, characteristic of a distinct, hierarchical landscape. Our paper is organized as follows: In the next Sec-tion II, we introduce the families of Ising spin models we employ in our study. In Sec. III, we will discuss RD and the measures we will apply to detect record fluctuations. In Sec. IV, we present the results of our investigation, and we conclude in Sec. V.
II. MODELS
Ising spin systems, consisting of spin variables σi =
±1, have been widely used, first of all as ferromagnets, to model spontaneous symmetry breaking and contin-uous phase transitions . With the random admix-ture of anti-ferromagnetic bonds, they have also served as models for disordered materials and glasses gener-ally [34, 35, 53, 54]. The relevance of such spin models reaches far beyond physics, into biological and sociologi-cal applications, for example . Here, we are employ-ing families of such spin models that interpolate between the randomly disordered spin glass on a cubic lattice, called the Edwards-Anderson model (EA) , as well as its mean-field version, the Sherrington-Kirkpatrick model (SK) , on one side and the respective homogeneous ferromagnetic systems on the other. Each system consists of a random mixture of ferromagnetic and anti-ferromagnetic bonds J between neighboring spins σi and
σj that are drawn from a distribution P (J) we have cho-sen to be bi-modal, i.e., Jij = ±J0, with energy units such that J0 = 1 in 3D and J0 = 1 /√N in the mean field case. A fraction p of ferromagnetic bonds is balanced out with a fraction 1−p of anti-ferromagnetic bonds such that
P (J) = pδ (J − J0) + (1 − p)δ (J + J0) . (1) For each, the Hamiltonian (without external field) reads
H = − ∑
〈ij 〉
Jij σiσj , (2) where 〈ij 〉 refers to all extant bonds between neighboring spins σi and σj , either on a cubic lattice for EA or all mutual pairs of spins for SK. In the family EA of models we study on the cubic lat-tice [36, 51], we change the admixture of bonds by varying
p between 12 ≤ p ≤ 1, from the pure glass with an equal mix of bonds ( p = 12 ) to a pure ferromagnet when all bonds are ferromagnetic ( p = 1 ). The situation is more complicated for SK, where already a sub-extensive excess of ferromagnetic bonds, away from the pure glass, results in ferromagnetic behavior. Specifically, since all N spins are mutually connected, there are 12 N (N − 1) bonds, and it only takes an imbalance between either type of bond, merely of order v √N , to achieve ferromagnetic ordering. Thus, we define a family of mean-field models parametrized by α with p = 12 + α√N , varying between
0 ≤ α ≤ 2 to explore the full range of behaviors .
III. AGING AND RECORD DYNAMICS A. Simulation of Quenches in Spin Glasses
The distinction between slow relaxation in glassy ver-sus homogeneous systems is succinctly analyzed in the simplest conceivable protocol of a hard quench from an 3E1
E3
E5
B3
B5
E4
B4
E2
B2B1
Figure 1. Illustration of the definition of valleys. The trace through an energy landscape produces a time sequence of en-ergy records ( Ei) and of barrier records ( Bj), relative to the most recent “ Ei” [30, 31]. Only the highest and lowest records of the “ Ei" and “ Bj”are kept to give a strictly alternat-ing sequence “ . . . Ei0Bj1Ei1Bj2Ei2. . . ”. Then, any sequence “Bj1Ei1Bj2” demarcates a valley (vertical lines).
easily equilibrated high-temperature state into an or-dered phase, whether glassy or ferromagnetic, crossing a phase transition in the process. Such a pure ag-ing protocol has been studied extensively in the last 40 years [33, 44, 48, 57, 58]. In this process, the system is thrown far out of equilibrium, left with an enormous amount of excess heat to be released to the bath to be able to descent deeper into its energy landscape to reach states with the appropriate (equilibrium) energy. To facilitate such a quench for the family of Ising spin models considered in our study, for each instance at time
t = 0 , we initiate with randomly assigned spins, either
σi = ±1, which corresponds to T = ∞, and run the sim-ulation for t > 0 at a low, finite temperature. For our family of models on the cubic lattice, the critical temper-ature for a transition into an ordered state varies from
Tc ≈ 1.1J0 in EA , to about Tc ≈ 4.5J0 for the ferro-magnet . In our Monte Carlo simulations, we quench to Tq = 0 .7J0 for all p, similar to Ref. , and monitor the aging process for about 10 5 sweeps. For the fam-ily of mean field models, we only vary the admixture of ferromagnetic bonds minutely, so that the transition tem-perature does not deviate much from that of SK, which is known to be Tc = J0 . Here, we also quench to
Tq = 0 .7J0 throughout. For each value of p in our study, we have averaged results over at least 10 4 realizations.
B. Valleys in an Energy Landscape
Key to our analysis of coarsening versus glassy relax-ation is the definition of a measure that can serve to distinguish the effect of fluctuations on the irreversible events by which a system relaxes. One such measure has been provided by Dall and Sibani in Ref. . There, the internal energy of an entire system of finite size is mon-itored to observe its time-trace for the ensuing quench. Since the system is expelling energy into the bath to re-lax, on average, the energy gradually decreases, albeit via localized, intermittent events , in line with experi-mental observations of glassy systems [43, 62–64]. In par-ticular, record-sized fluctuations are needed for a glassy system to relax, according to RD [46, 47]. As illustrated in Fig. 1, Dall and Sibani defined the “valley” production as an observable. in the follow-ing way: Let E be the up-to-now lowest energy value encountered up to time t and let E(t) be the instan-taneous energy. In turn, let the “barrier” B be the up-to-now highest energy attained, relative to the most recent E, i.e., B = E(t) − E. An energy trace then maps into a random sequence of symbols, like in Fig. 1,
. . . E1B1B2B3E2E3B4B5E4E5 . . . . Note that the trace can generate a sub-sequence of records in the lowest en-ergy, i.e., multiple E’s in a row, before it encounters its next higher (record) barrier B, and also a sub-sequence of such B’s before it meets the next E, and so on. Clearly, it is the latest E or B in either type of sub-sequence that is significant: Each prior one is merely transitory, while the last one supersedes each prior one as record that reaches its ultimate significance only after a new record fluctuation in the opposite direction is attained. Thus, we squash the entire sequence into a strict alternation between E and B, as the stricken letters in Fig. 1 imply, which then yield: . . . E1B3E3B5E5 . . . . Then, a “valley” is defined as the part of the trace between two consecutive record barrier-crossings, as indicated by vertical dashed lines there. If the ground state were to be reached, i.e., no further energy minimum could be found, the sequence would terminate, of course. To focus truly on locally correlated record barrier crossings, it would be useful to refine this definition of valley . However, unless a system gets too large, with too many simultaneous but spatially distant quakes, by considering a small enough system these events become sufficiently rare to dominate the fluctuations in the entire system trace, instead of being “washed out” by overlap-ping ones. This point illustrates also that, to understand a thermodynamic system out-of-equilibrium , it is often
not helpful to take the thermodynamic limit. Examples of a valley sequence from our simulations is shown for single energy traces in Fig. 2 for the EA spin glass (top) and the corresponding ferromagnetic system (bottom) on a cubic lattice. These plots exemplify the stark difference in the effect of fluctuations on either type of system that we discuss in the following. 4-1.78
Energy Density
Spin Glass (EA) Energy Density Random Ferromagnet
Figure 2. Typical trajectories of an aging process through the energy landscape of the spin glass model on a 3d -lattice with
L3= 16 3spins and a fraction pof ferromagnetic bonds and
1−panti-ferromagnetic bonds, here with p= 0 .5(top) and
p= 0 .85 (bottom). Energy ( H) and barrier ( N) records, as defined in Fig. 1, are marked along each trajectory, where the vertical dashed lines indicate the transition between consecu-tive valleys. While the energy decreases, on average, gradually as a logarithm in time with an ongoing but random produc-tion of further records in the glassy case ( p= 0 .5), the more ferromagnetic system ( p= 0 .85 ) expels energy in a few large events which appear to be triggered by typical fluctuations, record-sized fluctuations are seemingly irrelevant.
C. Dynamics Driven by Record-Sized Fluctuations
As alluded to in the introduction, glassy and other-wise homogeneous systems such as a ferromagnet distin-guish themselves in the manner fluctuations affect their relaxation dynamics. In the latter, barriers are compa-rably low and remain invariant independent of the depth within the landscape and, thus, of the age of the process. As Fig. 2 exemplifies, large releases of energy are pre-ceded by typical fluctuations at any stage of the process. Fewer events, like the evaporation of a domain in coars-ening, happen not because individual events become so much harder but rather because so many fewer events can happen when only few domains is left. Larger domains may take a little more time to evaporate, as meandering interfaces need to find each other and collide, but such an entropy barrier does not dominate the otherwise domain-size independent energetic barriers . Yet, ordinary fluctuations suffice to bring those interfaces together. In the glassy system, however, it is the barrier height growing with domain size that decelerates the event-rate. Although many domains remain available even after a long aging time, few muster the chance fluctuation re-quired to break up. In a landscape with those barriers, ordinary fluctuations become ineffective to drive the re-laxation process. They merely “rattle” the system during increasingly longer quasi-equilibrium interludes. Only rare, extraordinary large, in fact, record-size fluctuations manage to scale such barriers to expel excess heat, ad-vance the relaxation, and grow domain size, minutely. These features, widely shared across many disordered materials, have inspired the phenomenological descrip-tion at the basis of RD . The definition of valleys in the preceding section provides an especially adapt mea-sure for this phenomenology. In RD, the relaxation pro-cess of a non-equilibrium system after a hard quench is determined by large (i.e., record-sized), irreversible fluc-tuations which move the system from one meta-stable state to the next (usually only marginally more sta-ble than the last one) within its complex energy land-scape [46, 66]. This can be thought of as the system overcoming energy barriers in a hierarchical energy land-scape [37–41]. The rate λ(t) of such record events, also termed “quakes”, decelerates with time as 1/t . Hence, the expected number of events in a time interval [ t, tw], is
〈n(t, t w)〉
t
ˆ
tw
λ (t′) dt ′ ln
( ttw
)
(3) implying that the dynamics of the system is self-similar in the logarithm of time. That time-homogeneity is a common feature of many aging systems [44, 57, 67]. In our studies here, we are more concerned with the rate of events λ(t) and the logarithmic growth of observables in time. The dependence on waiting time tw has been the focus elsewhere [46, 61, 66].
IV. NUMERICAL RESULTS A. Edwards-Anderson Model
Applying the measure of a valley number defined in Sec. III B to the cubic Ising spin model introduced in Sec. II provides a notable distinction between glassy and homogeneous coarsening behavior, as Fig. 3 shows. For all p < p c ≈ 0.77 , the critical threshold found in Ref. , we find that the valley count progresses logarithmically in time (in fact, like the root of that logarithm ), consis-tent with Eq. (3). For larger values of p, the valley count slows ever more significantly to eventually plateau at a finite value, apparently. All the results shown here were obtained for systems with N = 16 3 = 8096 spins, using 510 1 10 2 10 3 10 4
Sweeps
1
2
3
4
5
6
7
8
9
10
11
12
Valleys
p = 0.5
p = 0.55
p = 0.6
p = 0.65
p = 0.7
p = 0.75
p = 0.8
p = 0.85
p = 0.9
p = 0.95
p = 1.0
Figure 3. Average number of valleys in EA, as defined in Fig. 1, that are traversed with time after a quench to
T = 0 .7J0 in a Ld = 16 3 spin glass with a fraction p of ferromagnetic bonds and 1 − p anti-ferromagnetic bonds. For
p ≤ 0.75 , the generation of valleys evolves essentially inde-pendent of p, while for a larger admixture of ferromagnetic bonds valley generation progresses to cease ever more rapidly and the number of valleys reached plateaus. 10 1 10 2 10 3 10 4
Sweeps
0
0.2
0.4
0.6
Magnetization
p = 0.5
p = 0.55
p = 0.6
p = 0.65
p = 0.7
p = 0.75
p = 0.8
p = 0.85
p = 0.9
p = 0.95
p = 1.0
Figure 4. Average magnetization per spin in EA, 〈m〉, ob-served with time after a quench during the ensuing aging process, as described in Fig. 3. Like there, systems with
p ≤ 0.75 behave glassy in a p-independent manner with little discernible magnetic ordering, while the more ferromagnetic systems become increasingly more ordered.
periodic boundaries, since we found very little variation with system size for larger N .The fact that the underlying ordered state is either glassy or ferromagnetic affords us to also measure the increase in magnetization with time, as demonstrated in Fig. 4. This measure actually exhibits a more dramatic transition between the glassy and the ferromagnetic case, as consecutive snapshots of both, the valley count as well as the magnetization, are shown in Fig. 5 for a progres-sion of times that increases by a factor of 8. In these plots, we have also marked the zero-temperature transi-tion at pc ≈ 0.77 , which proves consistent asymptotically 0.5 0.6 0.7 0.8 0.9 1
density p
0
0.2
0.4
0.6
2
4
6
8
10
12
Valleys
t = 2 14
t = 2 11
t = 2 8
Figure 5. Finite-time snapshots for EA of the numbers of valleys generated (top) and the corresponding magnetization per spin, 〈m〉 (bottom), as a function of ferromagnetic bond fraction p for three different times, taken from the data at T =0.7J0 shown in Fig. 3 and Fig. 4, respectively. The vertical line at pc = 0 .77 indicates the zero-temperature transition found in Ref. between a glassy and a ferromagnetic phase. 10 1 10 2 10 3 10 4
Sweeps
10 -3
10 -2
10 -1
10 0
10 1
10 2
10 3
Event Rate p = 0.5
p = 0.55
p = 0.6
p = 0.65
p = 0.7
p = 0.75
p = 0.8
p = 0.85
p = 0.9
p = 0.95
p = 1.0
Figure 6. Instantaneous rate of record barrier crossing events in EA, as defined in Fig. 1, with time after the quench, as described in Fig. 3. Asymptotically, for larger times, that rate varies as a power-law with a seemingly hyperbolic decline,
∼ 1/t (dotted line), for all p < 0.75 to an almost quadratic decline, ∼ 1/t 2 (dash-dotted line), for larger p.
with the transition out of the glassy relaxation behavior. Finally, we can also look at the instantaneous rate of barrier crossing events, effectively the derivative of the valley production, i.e, inverting the integral in Eq. (3). Indeed, throughout the glassy regime, the rate deceler-ates roughly hyperbolically, in accordance with the RD predictions. [Note that this could miss a minor logarith-mic correction, such as λ(t) ∼ 1/(t√ln t), for instance, needed to get √ln t for the valley production in Fig. 3.] For p > p c, in the ferromagnetic coarsening regime, we notice that the rate falls off increasingly sharper, ulti-mately about as ∼ 1/t 2. Consequently, its integral stalls 6
Figure 7. Number of valleys traversed during relaxation en-suing after a quench of SK for different bond fractions αfrom a high temperature T=∞to T= 0 .7J0, averaged over an ensemble of trajectories for N= 2048 spins. In the range
0.0≤α≤0.6,the number of valleys traversed grows loga-rithmically and largely independent of α, indicating that the regime is glassy.
out into the plateaus seen in Fig. 3. Apparently, do-main mergers occur more rapidly, on a power-law scale, in coarsening ferromagnets. Despite the rapid drop in the event rate, the average domain size manages to in-crease as a power-law , because later mergers expel larger amounts of excess heat, see Fig. 2. In case of the glass, each event expels on average a fixed amount of heat, roughly. Therefore, both valley production and domain growth proceed similarly (logarithmically), as an integral of the event rate, since each activation has the same impact.
B. Sherrington-Kirkpatrick Model
Using the valley counts defined in Sec. III B as an or-der parameter, we find a clear transition from a glassy regime to a ferromagnetic one in the mean field as well. However, unlike for EA on a cubic lattice, extending the neighborhood of each spin to all others in the case of SK changes the dynamics, and we have to explore the critical threshold at which the spin glass to ferromag-netic transition takes place on a different scale. Mutual connections between all spins require the number of fer-romagnetic bonds to only slightly exceed the number of antiferromagnetic bonds, in order to tip the system into becoming ordered. The transition to the ferromagnetic regime occurs almost immediate beyond a bond density of p = 0 .5, with a strong system size dependence, forcing us to adapt a different scale to observe it. To properly describe the behavior of SK, we therefore reparametrize the bond density in terms of α via p = 12 + α√N . Then, within the range of 0 ≤ α ≤ 2.0, we can localize a tran-sition that varies only slowly with size.
Figure 8. Average magnetization for SK in the same simula-tions shown in Fig. 7. According to this measurement, the system begins to order at αc≈0.6, since a non-zero magne-tization in the long-time limit indicates that majority of the spins have ferromagnetically ordered. The transition in mag-netization shown here is far more dramatic than in the valley counts, but nevertheless affirms the same critical threshold.
Figure 9. Instantaneous average valley counts and magneti-zation in SK as function of αat different sweep-times t= 16 ,256 and 4096 from left to right, each for three different system sizes indicated on the legend. The first row shows the aver-age number of valleys, and the second row shows the average magnetization. According to this data, the valley production is time dependent as the sharpness of the transition becomes more pronounced in the later sweeps. In contrast, the magne-tization appears to be saturated already early on, predicting the critical threshold within 16 sweeps. Additionally, we see no system size effects when using αas the parameter.
Similar to Fig. 3 for EA, in Fig. 7 we show the numbers of valleys found in a SK system with N = 2048 spins. There appears to be a critical threshold at αc ≈ 0.6. For α ≤ 0.6, the valley production increases about as log (t), essentially uniform with bond density, given the nearly perfect overlap in the data. This is no longer case when α > 0.6, where the production of valleys decreases gradually before plateauing completely. While domains in the sense of geometric regions of a certain length do not exist in a mean field system with long-range interactions, individual spins develop clusters of increasingly ordered 7
Figure 10. Instantaneous rates for the number of record bar-rier crossings as a function of time, for every α-value in SK. The instantaneous rate decreases as a power-law for all but the highest admixture values. In the glassy regime, the de-celerations is essentially hyperbolic (dotted line), while the rate drops more sharply for α > 0.6, up to roughly t−1.5
at α= 1 .6(dash-dotted line), beyond which further record events become immeasurably rare.
local fields with some of their neighbors that entrench the system into deeper valleys. It becomes increasingly more difficult for the system to overcome the energy barrier of flipping the entire cluster, causing the relaxation process to evolve logarithmically . That said, evidence of a critical threshold suggests that beyond αc, the system changes its landscape dramati-cally. It exhibits an inclination to order rapidly, facil-itated by the fact that local fields of individual spins immediately affect all others, as the evolution of mag-netization in Fig. 8 suggests. Flat interfaces between such clusters, as they may exist between domains in low-dimensional lattices like EA, are absent here and any imbalance in size quickly erodes inferior clusters. Therefore, despite the quantitative differences pertaining to local structure between the Edwards-Anderson and Sherrington-Kirkpatrick spin glass, our results suggest that the glassy behavior in both can be attributed to the hierarchical nature of the energy landscape, and the lack of it beyond the transition to ferromagnetic order, seen both in Fig. 4 and Fig. 8. We have also checked the evolution of valley counts across different system sizes and found only a minimal dependence of the transition on larger size, as shown in Fig. 9. While the relationship (or lack thereof) between the number of valleys encountered and the bond admix-ture exhibits time dependence, the critical threshold with regard to ordering already emerges after about two hun-dred sweeps. There is clearly an agreement between val-ley statistics and the ferromagnetic order parameter in suggesting αc ≈ 0.6 as the critical threshold. Lastly, we look at the deceleration of the rate of record barrier crossing events in Fig. 10. As shown in Fig. 6for the Edwards-Anderson model, the rate decays with a power of time t. While there is a steeper decelera-tion in the barrier crossing events for larger α-values, the difference between the exponents is quite subtle on this time scale within our simulations. In the glassy regime,
α < α c ≈ 0.6, the rate clearly decays hyperbolically, whereas it falls off steeper above αc. However, for values
α > 1.6, the fall-off becomes so significant that new val-leys are not encountered beyond the first ∼ 100 sweeps.
V. CONCLUSION
Our study explores the distinction between glassy re-laxation and ordinary coarsening, which is often ignored in the description and analysis of aging systems. Focus-ing on families of models that interpolate between either extreme, we not only apply measures [30, 31] that clearly indicate the difference but also show a rather sharp tran-sition in the non-equilibrium behavior between those ex-tremes that, for the Edwards-Anderson model on a cu-bic lattice, appears to coincide with the (equilibrium) zero-temperature transition between spin glass and fer-romagnet . The corresponding transition we find at a sub-extensive scale in SK seems to have been unnoticed. While the distinction we are making between a coars-ening (ferromagnetic) and an aging (glassy) regime can be seen as semantic, considering that both, algebraic as well as logarithmic growing domains, are commonly portrayed as coarsening , the difference in dynamic behavior after a quench is profound. The picture that emerges is one of a largely convex landscape on one side with invariant energetic barriers in the case of coarsening, a system that despite its often complex network of frac-tal interfaces locally homogenizes rather quickly. On the other side, we find a hierarchical landscape [37–41] with energetic (and potentially entropic) barriers that grow with deeper entrenchment within the landscape, render-ing all but record fluctuations ineffective for relaxation.
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Succumbed Sentence Examples
He looked to Sarah, who had also succumbed to the craving.
The readiness with which the American Indian succumbed to disease is well known.
He seems to have touched at the island of Tortugas, so named on account of the large number of turtles found there, and to have landed at several places, but many of his men succumbed to disease and he himself was wounded in an Indian attack, dying soon afterward in Cuba.
Dresden was the last great victory of the First Empire, By noon on the 27th August the Austrians and Russians were completely beaten and in full retreat, the French pressing hard behind them, but meanwhile Napoleon himself again succumbed G Beereri B eip \ ii g?
The Ionians in turn succumbed to the Dorians of Argos, who, according to the legend, were led by Deiphontes; and from that time the city continued to preserve its Dorian character.
Or maybe he'd succumbed to the weird draw around the woman.
In 1849 Garibaldi's wife Anita, who had accompanied him on his retreat from Rome, succumbed to fatigue in the marshes near Ravenna.
They succumbed to the Persian dynasty of the Sassanids, who ruled successfully for about four centuries, established the Zoroastrian faith as their state religion, and maintained a creditable conflict with the East Roman empire.
In the crypt is the grave of a traveller, who succumbed to excessive drinking of the local wine known as Est, est, est.
When Caesar invaded Britain 54 B.C. they joined him against their domestic rivals and it is possible (though not certain) that half a century after Caesar's departure they succumbed to them.
In Prussia at least the medieval system of local self-government had succumbed completely to the centralizing policy of the monarchy, and when it was revived it was at the will and for the purposes of the central authorities, as subsidiary to the bureaucratic system.
At least, she'd thought this until Dusty succumbed to it.
But they succumbed before the advance of the Medo-Persian power in 606 B.C., whereas it was not till 555 that Cyrus took Babylon.
In 1644 the Ming succumbed to the attacks of the Manchus, a northern tribe who captured Peking and founded the present imperial house.
Later, it allied itself with the Mongols and fought against the Mamelukes, to whom, however, it finally succumbed in 1375.
During the later part of their history they were in continual contact with Assyria, and, as a Syrian power, and perhaps also as a Cappadocian one, they finally succumbed to Assyrian pressure.
In the middle ages Arezzo was generally on the Ghibelline side; it succumbed to Florence in 1289 at the battle of Campaldino, but at the end of the century recovered its strength under the Tarlati family.
The rationalist spirit is, of course, coeval with human evolution; religion itself began with a rational attempt to maintain amicable relations with unknown powers, and each one of the dead religions succumbed before the development of rationalist inquiry into its premises.
The Lombard princes, who had frequently defended their city against the Saracens, succumbed before Robert Guiscard, who took the castle after an eight months' siege and made Salerno the capital of his new territory.
Under such disheartening conditions it is not surprising that this body was totally unable to cope with Sickingens insurrection, and that a few weeks after its meeting at Nuremberg in 1524 it succumbed to a series of attacks and disappeared from the history of Germany.
The despotate of Epirus succumbed in 1449, the duchy of Athens in 1456; in 1453 Constantinople was taken and the decrepit Byzantine empire perished; the greater part of Bosnia submitted in 1463; the heroic resistance of the Albanians under Scanderbeg collapsed with the fall of Croia (1466), and Venetian supremacy in Upper Albania ended with the capture of Scutari (1478).
It was, perhaps inevitable; when Patrick Stewart's Shakespearean-trained voice intoned the opening voiceover, most of us quickly succumbed.
That's how long my little prize remained with me until my darling succumbed to the trials and tribulations of life on the road, with me.
Monty, as he became known during his brief public life, succumbed to his injuries.
There are still many magneto exchanges in existence, but when new exchanges are erected only the very smallest are equipped for magneto working, that system having succumbed to the common battery one in the case of all equipments of moderate and large dimensions.
During the milder interglacial period some southern types, such as Rhododendron ponticum, still held their own, but ultimately succumbed.
During his brief reign he set on foot some domestic reforms, and sought to revive the authority of the senate, but, after a victory over the Goths in Cilicia, he succumbed to hardship and fatigue (or was slain by his own soldiers) at Tyana in Cappadocia.
And so the old limitations of Israel's popular religion, - the same limitations that encumbered also the religions of all the neighbouring races that succumbed in turn to Assyria's invincible progress, - now began to disappear.
Two assaults were repulsed after hours of hand-to-hand fighting; and when, after a fresh bombardment, the garrison saw that their case was hopeless, they killed their women and children, and only succumbed at last to a third assault because every man of them was either killed or mortally wounded.
The anxiety, fatigue and cold to which he was thus exposed, affecting a constitution naturally weak, laid the foundation of the disease to which he afterwards succumbed.
This spirit gave way to the physicians, who regarded " chemistry as the art of preparing medicines," a denotation which in turn succumbed to the arguments of Boyle, who regarded it as the " science of the composition of substances," a definition which adequately fits the science to-day.
During the wars of the French Revolution, it was taken by Dumouriez in 1793, evacuated soon after and retaken by Pichegru in 1795, after the whole of Holland had already succumbed to the French.
These were no longer numerous, many having succumbed to the hardships and sufferings of all kinds to which they had been exposed.
Walton illustrates Herbert's kindness to the poor by many touching anecdotes, but he had not been three years in Bemerton when he succumbed to consumption.
The compatibility of Christian and later Neo-Platonic ideas is evidenced by the writings of Synesius, bishop of Ptolemais, and though Neo-Platonism eventually succumbed to Christianity, it had the effect, through the writings of Clement and Origen, of modifying the tyrannical fanaticism and ultradogmatism of the early Christian writers.
They only succumbed when the weight of the archduke Maximilian was thrown into the scale against them (1484).
But little by little he succumbed to his milieu, the atmosphere of false confidence and passivity created around him by Alexeiev.
In 1899 her grandson, the hereditary prince of Coburg, had succumbed to phthisis, and in 1900 his father, the duke of Coburg, the queen's second son, previously known as the duke of Edinburgh, also died (July 30).
Sadik Beg soon repented of having asked for a Khoja, and eventually marched against Kashgar, which by this time had succumbed to Buzurg Khan and Yakub Beg, but was defeated and driven back to Khokand.
Why Neoplatonism succumbed in the conflict with Christianity is a question which the historians have never satisfactorily answered.
In 1 453 the king succumbed, Alvaro was arrested, tried and condemned by a process which was a mere parody of justice, and executed at Valladolid on the 2nd of June 1453.
The Hohenstaufen succumbed to it, and the papacy itself received a terrible shock, which shook its vast empire to the foundations.
The Arab tribes in Mesopotamia were Christian, and Heraclius at Edessa hoped for their support; but Karkisiya and Hit succumbed (636), and then Tekrit; and Heraclius retired to Samosata.
He succumbed to pressure from the boss.
Meanwhile the other independent principalities of Gondwana had in turn succumbed.
Lavoisier adequately recognized and acknowledged how much he owed to the researches of others; to himself is due the co-ordination of these researches, and the welding of his results into a doctrine to which the phlogistic theory ultimately succumbed.
But can a historian separate the opinions which rose to authority in the church from the other opinions which succumbed?
Three more of her children, as well as her husband, quickly caught the disease, and the youngest, "May," succumbed on the 16th.
The sultan's policy had been consistently directed to crushing the overgrown power of his vassals; in the spring of 1831 two rebellious pashas, Hussein of Bosnia and Mustafa of Scutari, had succumbed to his arms; and, since he was surrounded and counselled by the personal enemies of the pasha of Egypt, it was likely that, so soon as he should feel himself strong enough, he would deal in like manner with Mehemet Ali.
On the return journey Dr. Wulff and Olsen succumbed to the privation of scanty food and bad weather, and the survivors had difficulty in reaching Etah.
It succumbed to the Indo-Scythian Empire of the Kushana, who had obtained the sovereignty of Bactria as early as about A.D.
Julian pressed forward to Ctesiphon but succumbed to a wound; and his successor Jovian soon found himself in such straits, that he could only extricate himself and his army by a disgraceful peace at the close of 363, which ceded the possessions on the Tigris and the great fortress of Nisibis, and pledged Rome to abandon Armenia and her Arsacid protg, Arsaces III., to the Persian.
Eventually he succumbed to a conspiracy of his magnates, at whose head stood the general Bahram Cobin, who had defeated the Turks, but afterwards was beaten by the Romans.
The historical bent thus given to the drama was continued by the versatile Mendes Leal, by Gomes da Amorim and by Pinheiro Chagas, who all however succumbed more or less to the atmosphere and machinery of ultra-Romanticism, while the plays of Antonio Ennes deal with questions of the day in a spirit of combative liberalism.
At the very outset of a promising career he suddenly succumbed to an attack of smallpox on the 6th of November 1650, his son William III.
During the Northern War between Sweden and Russia, it was courageously defended (1700), but after the battle of Poltava it succumbed, and was taken in July 1710 by the Russians.
Such was the situation when the president, early in July 1850, was stricken by the disease to which he succumbed on the 9th.
The kingdom probably succumbed to the Huns established in the neighbourhood.
His election to the papacy, on the 29th of October 1591, was brought about by Philip II., who profited little by it, however, inasmuch as Innocent soon succumbed to age and feebleness, dying on the 30th of December 1591.
This disaster, though partly retrieved in the campaign of the following year, had a serious effect upon his vitality; henceforth he declined in health and in 1180 succumbed to a slow fever.
About 250 B.C. Diodotus (Theodotus), governor of Bactria under the Seleucidae, declared his independence, and commenced the history of the Greco-Bactrian dynasties, which succumbed to Parthian and nomadic movements about 126 B.C. After this came a Buddhist era which has left its traces in the gigantic sculptures at Bamian and the rock-cut topes of Haibak.
He strongly upheld in the House of Commons the measures taken, first by Mr. Macpherson and then by Sir Hamar Greenwood, to restore law and order in that country; and definitely refused to interfere in the case of the Lord Mayor of Cork who, sentenced to imprisonment for conducting a rebel organization, went on hunger-strike and eventually succumbed in gaol.
When the Carrara family succumbed in 1405, Este voluntarily surrendered to Venice and was allowed its independence, under a podesta; and thenceforth it followed the fortunes of Venetia.
But by the middle of October the Chinese army was decisively defeated; Peking was occupied; those British and French prisoners who had not succumbed to the hardships of their confinement were liberated.
A year later the Emperor was stricken down by illness, and succumbed to it on July 30 1912.
By 1208, however, the Kadambas had been overthrown by the Rattas, who in their turn succumbed to the Yadavas of Devagiri in 1250.
But two weeks after his arrival he succumbed to dysentery, and was buried at the age of eighty-three in the church of the Annunziata.
On the 15th of July 1895 he was attacked and barbarously mutilated by a band of Macedonian assassins in the streets of Sofia, and succumbed to his injuries three days later.
For a time he thought of responding to the appeal of some of the Polish revolutionaries, but Warsaw succumbed (September 1831) before he could set out.
A man of action and not of cunning shifts, he succumbed on the 10th of July to the blows of his own government, which had passed from his hands into those of Robespierre, his ambitious and crafty rival.
Politically moribund, it succumbed to the attacks of its virile southern neighbours, who, having emerged from foreign tutelage, developed according to the natural laws of their own genius and environment.
He had just become connected with the Revue de Paris, when his delicate constitution succumbed to a slight attack of illness on the 19th of October 1894.
Its northern and southern extremities have been named Cape Costigan and Cape Molyneux, in memory of two explorers who were among the first in modern times to navigate the sea and succumbed to the consequent fever and exhaustion.
The station succumbed to disrepair many years before is closed.
Mice in the study that received treatment remained healthy for almost a year after untreated mice succumbed to the disease.
The baby succumbed to illness suddenly just weeks after birth.
His cheerful demeanor succumbed to the stress of his bad marriage.
He succumbed to defeat.
She succumbed to heat stroke and awaits a new air conditioner to feel better.
He finally succumbed to his illness this past December.
I tried to resist but eventually succumbed and agreed to edit the paper.
Those without hats nearly succumbed to frostbite.
To educate a child regarding the dangers of alcohol was deemed more beneficial than waiting until they had succumbed.
In 1996, Monsanto's pest-resistant Bt-cotton succumbed to a heat wave in the southern US and was destroyed by bollworms and other pests.
Now sadly it has succumbed to the competition of the chain bookstores.
Two bulbs have succumbed to a rot that luckily did not spread all through the whole potful.
Like many before him he has succumbed to the wallet draining world of high power rocketry and is UKRA Level 1 certified.
He died in 45 1; some years earlier Nestorius, the ex-patriarch, had succumbed perhaps to his persecution and to old age, in the neighbourhood of Akhmim.
Once Howie succumbed to slumber, his sleep was anything but peaceful.
Alice was a geranium Cynthia had lovingly rescued from certain death by frost last September when the rest of the couple's first-year garden succumbed to the advancing seasons.
Alice was a geranium Cynthia had lovingly rescued from certain death by frost last September when the rest of their first year garden succumbed to the advancing seasons.
In 1544 the Indians, so far as they had not succumbed to the labour of the mines and fields to which they were put by the Spaniards, were proclaimed emancipated.
So far the Hevea plantations in Ceylon and the East have not been seriously troubled by insect or fungoid pests, and those which have occurred have succumbed to proper treatment.
Soon after marriage his wife was attacked by a lingering illness, to which she succumbed, Lagrange devoting all his time, and a considerable store of medical knowledge, to her care.
At last he succumbed to the repeated requests of Girolamo or Geronimo Cardano, who swore that he would regard them as an inviolable secret.
He succumbed to leprosy on the 15th of April 1889.
He succumbed to fear and choked up.
He succumbed under the weight he had to carry.
The outcome depended on Bill Rice who unfortunately succumbed to defeat.
After the exodus, which perhaps took place about 1300 B.C., they moved northwards again and founded a state of modest dimensions, which attained a short-lived unity under Solomon, but succumbed to internal dissensions and to the attacks of Assyria and Babylon.
Shortly after his accession he was threatened with invasion by Cambyses, the Persian conqueror of Egypt, but (according to his own account) destroyed the fleet sent by the invader up the Nile, while (as we learn from Herodotus) the land-force succumbed to famine (see Cambyses).
It succumbed to the ceaseless alternation of tolerance and persecution which characterized the Arab rule in Egypt, and the mass of the Coptic people became unfaithful to the Church.
In spite of all their bravery, they succumbed to the Greek phalanx, when once the generalship of a Miltiades or a Pausanias had brought matters to a hand to hand conflict; and it was with justice that the GrecksAeschylus, for instance viewed their battles against the Persian as a contest between spear and bow.
On the fields of Marathon and Plataea, the Persian archers succumbed to the Greek phalarn of hoplites; but the actual decision was effected by Themistocles who had meanwhile created the Athenian fleet which at Salamis proved its superiority over the Perso-Phoenician armada, anc thus precluded beforehand the success of the land-forces.
Here the Graeco-Bactrian and Graeco-Indian kingdoms held their own, till, in 139 B.C., they succumbed before the invading Mongolian and Scythian tribes (see BACTRIA and works quoted there).
But this state of affairs was too insecure even for these rovers, and they would speedily have succumbed had not a refuge been found for them by the fortunate conquest of Jamaica in 1655 by the navy of the English Commonwealth.
The substation of SR origin formerly resided on the right, but had succumbed many years before the station 's closure.
When Christian ideas succumbed in the 18th century to rationalist ideas, feudal society fought its death battle with the then revolutionary bourgeoisie.
Mice in the 17 month study treated with mAbs remain clinically healthy almost a year after the untreated mice succumbed to the disease.
Sir Digby Jones, director general of the CBI, said the government has succumbed to pressure from the unions.
By the end, the hero of this story seems to have finally succumbed to defeat.
It succumbed to heat stroke on Monday and awaits ministration, and probably a new fan, in a dark corner of a room.
The chances are that, no appliances being at hand to assist him, he succumbed under the weight he had to carry.
He finally succumbed to his illness on 12 December.
I tried and tried and eventually succumbed to editing the kernel.
The outcome depended on Bill Rice who unfortunately succumbed to a straight set defeat.
Those with bob hats went home freezing those without nearly succumbed to frost bite of the ear lobes.
A few oft given reasons are crazy schedules or the relationship succumbed to the harsh light of the paparazzi's constant spotlight.
John Belushi - Another celebrity who succumbed to a drug overdose, this Saturday Night Live alum died in 1982 from a fatal injection of cocaine and heroin.
However, all of that changed once she succumbed to a well-publicized nose job that stalled her career instead of helping it.
Married in 1984, the pair only had five short years together before Radner succumbed to cancer.
McClanahan was a breast cancer survivor, but succumbed to a stroke on June 3, 2010.
After their father's defrocking and the divorce of their parents, the brothers abandoned the road in favor of Nashville where they succumbed to the forbidden allure of music and began collaborating with songwriter Angelo Petraglia.
Many people do not understand when they should get help for someone that has succumbed to alcohol poisoning.
Henry, who had stayed behind with his injured girlfriend, eventually succumbed to the heat, as did she.
While other trailers succumbed to the economic woes of the World War II era, the Airstream endured although its luxury label meant that few of its motor homes were sold.
Some are open to the public, while others are either closed to the public - sometimes they still exist as private residences - or have succumbed to the demands of time and progress.
The painter, knowing that making such an agreement with such an evil entity was the wrong thing to do, succumbed to his desperate greed and accepted the offer.
Unfortunately, flash has succumbed to a lot of bootlegging in recent years.
An example of this was Pedro Zamora, who was openly homosexual during filming of the San Francisco house, and eventually succumbed to AIDS in 1994, after a long battle with the disease and plenty of activism credited to his name.
Of greater historical interest are the Chams, who are to be found for the most part in southern Annam and in Cambodia, and who, judging from the numerous remains found there, appear to have been the masters of the coast region of Cochin-China and Annam till they succumbed before the pressure of the Khmers of Cambodia and the Annamese.
The last Greek prince, Hermaeus, seems to have succumbed about 30 B.C. It was just at this time that the Graeco-Roman world of the West was consolidated as the Roman Empire, and, though Greek rule in India had disappeared, active commercial intercourse went on between India and the Hellenistic lands.
Their sufferings on the route were dreadful; many succumbed and were abandoned.
As a fortress, Metz has always been of the highest importance, and throughout history down to 1870 it had never succumbed to an enemy, thus earning for itself the name of La pucelle.
After proclaiming his intention of conferring on his subjects the blessings of peace, he joined in 1798 an Anglo-Austrian coalition against France; but when Austria paid more attention to her own interests than to the interests of monarchical institutions in general, and when England did not respect the independence of Malta, which he had taken under his protection, he succumbed to the artful blandishments of Napoleon and formed with him a plan for ruining the British empire by the conquest of India.
In 1107 B.C., however, he sustained a temporary defeat at the hands of Merodach-nadin-akhi (Marduknadin-akhe) of Babylonia, where the Kassite dynasty had finally succumbed to Elamite attacks and a new line of kings was on the throne.
Here on the 28th of December 1825 he succumbed to the combined effects of climate and of opium.
She covered her eyes with one forearm and succumbed to tears.
Fierce opposition ensued, and the pari passu compromise was adopted to which reference is made in the section on Education above; Mr Savona was an able organizer, and began the real emancipation of the Maltese masses from educational ignorance; but he succumbed to agitation before accomplishing substantial results.
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Laguerre polynomials
From Encyclopedia of Mathematics
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Chebyshev–Laguerre polynomials
Polynomials that are orthogonal on the interval $ ( 0 , \infty ) $ with weight function $ \phi ( x) = x ^ \alpha e ^ {-x}$, where $ \alpha > - 1 $. The standardized Laguerre polynomials are defined by the formula
$$ L _ {n} ^ \alpha ( x) = \ \frac{x ^ {- \alpha } e ^ {x} }{n!} \frac{d ^ {n} }{dx ^ {n} } ( x ^ {\alpha + n } e ^ {-x} ) ,\ \ n = 0 , 1 , . . . . $$
Their representation by means of the gamma-function is
$$ L _ {n} ^ \alpha ( x) = \ \sum _ { k= 0}^{ n } \frac{\Gamma ( \alpha + n + 1 ) }{\Gamma ( \alpha + k + 1 ) } \frac{( - x ) ^ {k} }{k ! ( n - k ) ! } . $$
In applications the most important formulas are:
$$ ( n + 1 ) L _ {n+1} ^ \alpha ( x) = \ ( \alpha + 2n + 1 - x ) L _ {n} ^ \alpha ( x) - ( \alpha + n ) L _ {n-1} ^ \alpha ( x) , $$
$$ x L _ {n-1} ^ {\alpha + 1 } ( x) = ( n + \alpha ) L _ {n-1} ^ \alpha ( x) - n L _ {n} ^ \alpha ( x) , $$
$$ ( L _ {n} ^ \alpha ( x) ) ^ \prime = - L _ {n-1} ^ {\alpha + 1 } ( x) . $$
The polynomial $ L _ {n} ^ \alpha ( x) $ satisfies the differential equation (Laguerre equation)
$$ x y ^ {\prime\prime} + ( \alpha - x + 1 ) y ^ \prime + n y = 0 ,\ n = 1 , 2 , . . . . $$
The generating function of the Laguerre polynomials has the form
$$ \frac{e ^ {- x t / ( 1 - t ) } }{( 1 - t ) ^ {\alpha + 1 } } = \ \sum _ { n=0}^\infty L _ {n} ^ \alpha ( x) t ^ {n} . $$
The orthonormal Laguerre polynomials can be expressed in terms of the standardized polynomials as follows:
$$ \widehat{L} {} _ {n} ^ \alpha ( x) = (- 1) ^ {n} L _ {n} ^ \alpha ( x) \sqrt { \frac{\Gamma ( n + 1 ) }{\Gamma ( \alpha + n + 1 ) } } . $$
The set of all Laguerre polynomials is dense in the space of functions whose square is integrable with weight $ \phi ( x) $ on the interval $ ( 0 , \infty ) $.
Laguerre polynomials are most frequently used under the condition $ \alpha = 0 $; these were investigated by E. Laguerre , and are denoted in this case by $ L _ {n} ( x) $( in contrast to them, the $ L _ {n} ^ \alpha ( x) $ are sometimes known as generalized Laguerre polynomials). The first few Laguerre polynomials $ L _ {n} ( x) $ have the form
$$ L _ {0} ( x) = 1 ,\ L _ {1} ( x) = 1 - x , $$
$$ L _ {2} ( x) = 1 - 2 x + \frac{x ^ {2} }{2} , $$
$$ L _ {3} ( x) = 1 - 3 x + \frac{3 x ^ {2} }{2} - \frac{x ^ {3} }{6} , $$
$$ L _ {4} ( x) = 1 - 4 x + 3 x ^ {2} - \frac{2 x ^ {3} }{3} + \frac{x ^ {4} }{24} . $$
The Laguerre polynomial $ L _ {n} ^ \alpha ( x) $ is sometimes denoted by $ L _ {n} ( x ; \alpha ) $.
References
| | |
--- |
| | E. Laguerre, "Sur le transformations des fonctions elliptiques" Bull. Soc. Math. France , 6 (1878) pp. 72–78 |
| | V.A. Steklov, Izv. Imp. Akad. Nauk. , 10 (1916) pp. 633–642 |
| | G. Szegö, "Orthogonal polynomials" , Amer. Math. Soc. (1975) |
| | P.K. Suetin, "Classical orthogonal polynomials" , Moscow (1979) (In Russian) |
Comments
Laguerre polynomials can be written as confluent hypergeometric functions (cf. Confluent hypergeometric function) and belong to the classical orthogonal polynomials. They have a close connection with the Heisenberg representation: as matrix elements of irreducible representations and as spherical functions on certain Gel'fand pairs (cf. Gel'fand representation) associated with the Heisenberg group. See the references given in [a1], Chapt. 1, §9.
References
| | |
--- |
| [a1] | G.B. Folland, "Harmonic analysis in phase space" , Princeton Univ. Press (1989) |
How to Cite This Entry: Laguerre polynomials. Encyclopedia of Mathematics. URL:
This article was adapted from an original article by P.K. Suetin (originator), which appeared in Encyclopedia of Mathematics - ISBN 1402006098. See original article
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15107 | https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Organic_Chemistry_(Morsch_et_al.)/10%3A_Organohalides/10.02%3A_Preparing_Alkyl_Halides_from__Alkanes_-_Radical_Halogenation | Skip to main content
10.2: Preparing Alkyl Halides from Alkanes - Radical Halogenation
Last updated
: Mar 18, 2024
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10.1: Names and Properties of Alkyl Halides
10.3: Preparing Alkyl Halides from Alkenes - Allylic Bromination
Page ID
: 31495
Jim Clark, Steven Farmer, Dietmar Kennepohl, Layne Morsch, William Reusch, Kristen Kelley, & Britt Farquharson
LibreTexts
( \newcommand{\kernel}{\mathrm{null}\,})
Objectives
After completing this section, you should be able to
explain why the
radical
halogenation
of
alkanes
is not usually a particularly good method of preparing pure samples of alkyl halides.
2. use bond energies to account for the fact that in
radical
chlorinations, the reactivity of hydrogen atoms decreases in the order
3. predict the approximate ratio of the expected products from the monochlorination of a given alkane.
Study Notes
The following terms are synonymous:
methyl hydrogens, primary hydrogens, and 1° hydrogens.
methylene hydrogens, secondary hydrogens, and 2° hydrogens.
methine hydrogens, tertiary hydrogens, and 3° hydrogens.
Note that in
radical
chlorination reactions, the reactivity of methine, methylene and methyl hydrogens decreases in the ratio of approximately 5 : 3.5 : 1. This will aid in the prediction of expected products from the monochlorination of a given alkane.
Radical Halogenation
Alkanes (the simplest of all organic compounds) undergo very few reactions. One of these reactions is
halogenation
, or the substitution of a single hydrogen on the alkane for a single halogen (Cl2 or Br2) to form a haloalkane. This reaction is very important in
organic chemistry
because it functionalizes
alkanes
which opens a gateway to further chemical reactions.
General Reaction
Radical Chain Mechanism
The reaction proceeds through the
radical
chain
mechanism
which is characterized by three steps: initiation, propagation, and termination. Initiation requires an input of energy but after that the reaction is self-sustaining.
Step 1: Initiation
During the initiation step free radicals are created when ultraviolet light or heat causes the X-X halogen bond to undergo homolytic to create two halogen free radicals. It is important to note that this step is not energetically favorable and cannot occur without some external energy input. After this step, the reaction can occur continuously (as long as reactants provide) without input of more energy.
Step 2: Propagation
The next two steps in the
mechanism
are called propagation steps. In the first
propagation step
, a chlorine
radical
abstracts hydrogen atom from methane. This gives hydrochloric acid (HCl, the inorganic product of this reaction) and the methyl
radical
. In the second
propagation step
, the methyl
radical
reacts with more of the chlorine starting material (Cl2). One of the chlorine atoms becomes a
radical
and the other combines with the methyl
radical
to form the
alkyl halide
product.
Step 3: Termination
In the three termination steps of this
mechanism
, radicals produced in the
mechanism
an undergo
radical
coupling to form a sigma bond. These are called termination steps because a free
radical
is not produced as a product, which prevents the reaction from continuing. Combining the two types of radicals produced can be combined to from three possible products. Two chlorine radicals and couple to form more halogen reactant (Cl2). A chlorine
radical
and a methyl
radical
can couple to form more product (CH3Cl). An finally, two methyl radicals can couple to form a side product of ethane (CH3CH3).
This reaction is a poor synthetic method due to the formation of polyhalogenated side products. The desired product occurs when one of the hydrogen atoms in the methane has been replaced by a chlorine atom. However, the reaction doesn't stop there, and all the hydrogens in the methane can in turn be replaced by chlorine atoms to produce a mixture of chloromethane, dichloromethane, trichloromethane and tetrachloromethane.
Energetics
Why do these reactions occur? Is the reaction favorable? A way to answer these questions is to look at the change in enthalpy ΔH that occurs when the reaction takes place.
ΔH = (Energy put into reaction) – (Energy given off from reaction)
If more energy is put into a reaction than is given off, the ΔH is positive, the reaction is
endothermic
and not energetically favorable. If more energy is given off in the reaction than was put in, the ΔH is negative, the reaction is said to be
exothermic
and is considered favorable. The figure below illustrates the difference between
endothermic
and
exothermic
reactions.
ΔH can also be calculated using bond dissociation energies (ΔH°):
Let’s look at our specific example of the chlorination of methane to determine if it is
endothermic
or
exothermic
:
Since, the ΔH for the chlorination of methane is negative, the reaction is
exothermic
. Energetically this reaction is favorable. In order to better understand this reaction we need to look at the
mechanism
( a detailed step by step look at the reaction showing how it occurs) by which the reaction occurs.
Chlorination of Other Alkanes
When
alkanes
larger than ethane are halogenated, isomeric products are formed. Thus chlorination of propane gives both 1-chloropropane and 2-chloropropane as mono-chlorinated products. The
halogenation
of propane discloses an interesting feature of these reactions. All the hydrogens in a complex alkane do not exhibit equal reactivity. For example, propane has eight hydrogens, six of them being structurally equivalent primary, and the other two being secondary. If all these hydrogen atoms were equally reactive,
halogenation
should give a 3:1 ratio of 1-halopropane to 2-halopropane mono-halogenated products, reflecting the primary/secondary numbers. This is not what we observe. Light-induced gas phase chlorination at 25 ºC gives 45% 1-chloropropane and 55% 2-chloropropane.
CH3-CH2-CH3 + Cl2 → 45% CH3-CH2-CH2Cl + 55% CH3-CHCl-CH3
These results suggest strongly that 2º-hydrogens are inherently more reactive than 1º-hydrogens, by a factor of about 3.5:1. Further experiments showed that 3º-hydrogens are about 5 times more toward halogen atoms 1º-hydrogens. Thus, light-induced chlorination of 2-methylpropane gave predominantly (65%) 2-chloro-2-methylpropane, the substitution product of the sole 3º-hydrogen, despite the presence of nine 1º-hydrogens in the
molecule
.
(CH3)3CH + Cl2 → 65% (CH3)3CCl + 35% (CH3)2CHCH2Cl
The Relative Reactivity of Hydrogens to
Radical
Chlorination
This difference in reactivity can only be attributed to differences in C-H bond dissociation energies. In our previous discussion of bond energy we assumed average values for all bonds of a given kind, but now we see that this is not strictly true. In the case of carbon-hydrogen bonds, there are significant differences, and the specific dissociation energies (energy required to break a bond homolytically) for various kinds of C-H bonds have been measured. These values are given in the following table.
| R (in R –H) | methyl | ethyl | i-propyl | t-butyl |
--- ---
| Bond Dissociation Energy (kcal/mole) | 103 | 98 | 95 | 93 |
This data shows that a tertiary C-H bond (93 kcal/mole) is easier to break than a secondary (95 kcal/mole) and primary (98 kcal/mole) C-H bond. These bond dissociation energies can be used to estimate the relative stability of the radicals formed after homolytic cleavage. Because a tertiary C-H bond requires less energy to undergo homolytic cleavage than a secondary or primary C-H bond, it can be inferred that a tertiary
radical
is more stable than secondary or primary.
Relative Stability of Free Radicals
Exercise
Write out the complete
mechanism
for the chlorination of methane.
Answer
: The answer to this problem is actually above in the initiation, propagation and termination descriptions.
Exercise
Explain, in your own words, how the first
propagation step
can occur without input of energy if it is energetically unfavorable.
Answer
: Since the second step in propagation is energetically favorable and fast, it drives the equilibrium toward products, even though the first step is not favorable.
Exercise
Which step of the
radical
chain
mechanism
requires outside energy? What can be used as this energy?
Answer
: Initiation step requires energy which can be in the form of light or het.
Exercise
Having learned how to calculate the change in enthalpy for the chlorination of methane apply your knowledge and using the table provided below calculate the change in enthalpy for the bromination of ethane.
| | |
--- |
| Compound | Bond Dissociation Energy (kcal/mol) |
| CH3CH2-H | 101 |
| CH3CH2-Br | 70 |
| H-Br | 87 |
| Br2 | 46 |
Answer
: To calculate the enthalpy of reaction, you subtract the BDE of the bonds formed from the BDE of the bonds broken.
Bonds broken are C-H and Br-Br.
Bonds formed are H-Br adn C-Br.
Bonds broken - bonds formed = change in enthalpy
(101 kcal/mol + 46 kcal/mol) - (87 kcal/mol + 70 kcal/mol) = change in enthalpy
-10 kcal/mol = change in enthalpy for bromination of ethane.
Exercise
1) Predict the mono-substituted halogenated product(s) of chlorine gas reacting with 2-methylbutane.
2) Predict the relative amount of each mono-brominated product when 3-methylpentane is reacted with Br2. Consider 1°, 2°, 3° hydrogen.
3) For the following compounds, give all possible monochlorinated derivatives.
Answer
10.1: Names and Properties of Alkyl Halides
10.3: Preparing Alkyl Halides from Alkenes - Allylic Bromination |
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Human anatomy 2
Human anatomy 1
Human neuroanatomy
Axilla
Axilla
Definition
Muhammad A. Javaid
The axilla, also known as the arm pit, is a pyramid-shaped space situated below the shoulder joint. Its apex, called the axillary inlet, faces upwards, while the base, known as the floor, points downward. Inside the axilla there are numerous vessels, nerves, lymph nodes, and adipose tissue. It serves as a pathway for nerves and vessels to travel from the neck to the arm.
The axillary inlet has a triangular shape and is bounded by the first rib on the medial side, the clavicle anteriorly, and the superior border of the scapula and coracoid process posteriorly. The trunks of brachial plexus, subclavian artery, and vein cross over the first rib as they pass through the axillary inlet into the axillary space. Inside the axilla, the trunks branch into divisions and cords, while the subclavian vessels transform into the axillary artery and vein.
The axillary space is surrounded by anterior, posterior, medial, and lateral walls, which are formed by muscles or bone. For example:
The pectoralis major and minor muscles form the anterior wall, and the pectoralis major also creates the anterior axillary fold.
The subscapularis, teres minor, teres major, latissimus dorsi, and long head of triceps muscles form the posterior wall.
The serratus anterior muscle and upper ribs form the medial wall.
The intertubercular sulcus of the humerus forms the lateral wall.
Please note that the short head of the biceps and coracobrachialis, both inserting into the coracoid process of the scapula, also pass through and ascend in the axilla.
The main artery in the axilla is the axillary artery, which is a continuation of the subclavian artery. It exits the axilla (distal to the teres major muscle) to enter the arm where it becomes the brachial artery.
The primary nerve structure within the axilla is the brachial plexus, formed by the C5-T1 roots (or anterior rami) of spinal nerves. Its branches provide innervation to the axillary, shoulder, and upper limb regions. The innervation of axillary muscles is as follows:
The pectoralis major and minor muscles are innervated by the medial and lateral pectoral nerves (branches of the medial and lateral cords of the brachial plexus).
The serratus anterior muscle is innervated by the long thoracic nerve (derived from the C5, C6, C7 roots of the brachial plexus).
The coracobrachialis and short head of the biceps femoris muscles are innervated by the musculocutaneous nerve (a branch of the medial cord of the brachial plexus).
The subscapularis muscle is Innervated by the upper and lower subscapular nerves (branches of the posterior cord of the brachial plexus).
The teres major muscle is Innervated by the lower subscapular nerve (a branch of the posterior cord).
The latissimus dorsi muscle is Innervated by the thoracodorsal nerve (a branch of the posterior cord).
References
Gordon, A. and Alsayouri, K. Anatomy, Shoulder and Upper Limb, Axilla. [Updated 2022 Jul 25]. In: StatPearls [Internet]. Treasure Island (FL): StatPearls Publishing; 2022 Jan-. Available from:
Drake, R.L., Vogl, A.W. and Mitchell, A.W.M. (2009). ‘Chapter 7: Upper Limb’ in Gray’s anatomy for Students. (2nd ed.) Philadelphia PA 19103-2899: Elsevier, pp. 684-710.
Gordon, A. and Alsayouri, K. Anatomy, Shoulder and Upper Limb, Axilla. [Updated 2022 Jul 25]. In: StatPearls [Internet]. Treasure Island (FL): StatPearls Publishing; 2022 Jan-. Available from:
Drake, R.L., Vogl, A.W. and Mitchell, A.W.M. (2009). ‘Chapter 7: Upper Limb’ in Gray’s anatomy for Students. (2nd ed.) Philadelphia PA 19103-2899: Elsevier, pp. 684-710.
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15109 | https://www.m-hikari.com/ams/ams-2014/ams-169-172-2014/sustekAMS169-172-2014.pdf | Applied Mathematical Sciences, Vol. 8, 2014, no. 172, 8601 - 8609 HIKARI Ltd, www.m-hikari.com On Hessians of Composite Functions ˇ Cestm´ ır B´ arta, Martin Kol´ aˇ r and Jan ˇ Sustek Department of Mathematics, Faculty of Science The University of Ostrava, 701 03 Ostrava Czech Republic Copyright c ⃝2014 ˇ Cestm´ ır B´ arta, Martin Kol´ aˇ r and Jan ˇ Sustek.
This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Abstract In this paper we will study the Hessian matrices of composite func-tions F which are in the form F(x) = f(g(x)) with f : R →R and g: Rn →R. We present an explicit formulas for the Hessian of F and for the inverse of the Hessian matrix.
Mathematics Subject Classification: 26B05 Keywords: Hessian, composite function 1 Introduction For a function f : Rn →R the Hessian matrix Hf(x) is defined as the n × n matrix of the second-order partial derivatives, Hf(x) = ∂2f ∂x2 1 . . .
∂2f ∂x1∂xn .
.
.
...
.
.
.
∂2f ∂xn∂x1 . . .
∂2f ∂x2 n .
The determinant of the above matrix is called Hessian. The Hessian matrix plays an important role in many areas of mathematics.
It is important in neural computing, for instance several non-linear optimization algorithms used for training neural networks are based on considerations of the second-order properties of the error surface, which are controlled by the Hessian matrix .
8602 ˇ Cestm´ ır B´ arta, Martin Kol´ aˇ r and Jan ˇ Sustek The inverse of the Hessian matrix has been used to identify the least significant weights in a network as a part of network ‘pruning’ algorithms, or it can also be used to assign error bars to the predictions made by a trained network .
Hessian matrices are also applied in Morse theory .
Throughout this paper we will study the Hessian matrices of composite functions F which are in the form F(x) = f(g(x)) with f : R →R and g: Rn → R. We present an explicit formulas for the Hessian of F and for the inverse of the Hessian matrix. In previous years, several papers were published with such formulas, but only for special functions F, see e.g. or . These results follow easily from our general results.
We will use the following notation for simple work with vectors and matrices col a(i) = a(1) .
.
.
a(n) , row a(i) = a(1) . . .
a(n) , mat a(i, j) = a(1, 1) . . .
a(1, n) .
.
.
...
.
.
.
a(n, 1) . . .
a(n, n) , diag a(i) = a(1) 0 ...
0 a(n) .
Using this notation we have ∇g(x) = col ∂g ∂xi and I = diag 1 = mat δij , where δij is the Kronecker symbol, i.e. δii = 1 and δij = 0 for i ̸= j.
2 Results Our first result concerns the determinant of the Hessian matrix.
Theorem 1 Let f : R →R and g: Rn →R be real functions and let F(x) = f(g(x)) be their composition. Then the Hessian of the function F equals det HF(x) = 1 + f ′′(g(x)) f ′(g(x)) ∇g(x)T · Hg(x)−1 · ∇g(x) f ′(g(x))n det Hg(x) .
The following result concerns the inverse of the Hessian matrix.
Theorem 2 Let f : R →R and g: Rn →R be real functions and let F(x) = f(g(x)) be their composition. Then the inverse of the Hessian matrix of the function F equals HF(x)−1 = I − Hg(x)−1 · ∇g(x) · ∇g(x)T f′(g(x)) f′′(g(x)) + ∇g(x)T · Hg(x)−1 · ∇g(x) · Hg(x)−1 f ′(g(x)) .
On Hessians of composite functions 8603 Theorem 3 is a consequence of previous theorems for a particular class of functions g.
Theorem 3 Let αi ∈R for i = 1, . . . , n and let f : R →R be a real function.
Put g(x) = n Q k=1 xαk k and F(x) = f(g(x)). Then the Hessian of F equals det HF(x) = 1+g(x)f ′′(g(x)) f ′(g(x)) |α| |α| −1 f ′(g(x))n(−1)n+1(|α|−1) n Y k=1 αkxnαk−2 k , where |α| = n P k=1 αk. The inverse of the Hessian matrix is HF(x)−1 = 1 g(x)f ′(g(x)) mat 1 |α| −1− 1 f′(g(x)) g(x)f′′(g(x))(|α| −1)2 + |α|(|α| −1) −δij αi xixj .
Example 1 Chen considered function of the form F(x) = f n P k=1 hk(xk) and computed inductively its Hessian.
We obtain the same result directly using Theorem 1. We have g(x) = n P k=1 hk(xk). Hence ∇g(x) = col h′ i(xi) , Hg(x) = diag h′′ i (xi) , det Hg(x) = n Y k=1 h′′ k(xk) , Hg(x)−1 = diag 1 h′′ i (xi) .
Then Theorem 1 implies that det HF(x) = 1 + f ′′(g(x)) f ′(g(x)) row h′ i(xi) · diag 1 h′′ i (xi) · col h′ i(xi) f ′(g(x))n n Y k=1 h′′ k(xk) = 1 + f ′′(g(x)) f ′(g(x)) n X k=1 h′ k(xk)2 h′′ k(xk) f ′(g(x))n n Y k=1 h′′ k(xk) .
Moreover, using Theorem 2, we obtain the inverse of the Hessian matrix.
HF(x)−1 = I − diag 1 h′′ i (xi) · col h′ i(xi) · row h′ i(xi) f′(g(x)) f′′(g(x)) + row h′ i(xi) · diag 1 h′′ i (xi) · col h′ i(xi) diag 1 h′′ i (xi) f ′(g(x)) = mat δij − h′ i(xi)h′ j(xj) h′′ i (xi) f′(g(x)) f′′(g(x)) + n P k=1 h′ k(x2 k) h′′ k(xk) !
· diag 1 f ′(g(x))h′′ i (xi) = mat δij − h′ i(xi)h′ j(xj) h′′ i (xi) f′(g(x)) f′′(g(x)) + n P k=1 h′ k(x2 k) h′′ k(xk) !
1 f ′(g(x))h′′ j(xj) 8604 ˇ Cestm´ ır B´ arta, Martin Kol´ aˇ r and Jan ˇ Sustek Example 2 Trojovsk´ y and Hlad´ ıkov´ a considered function F(x) = exp n Q k=1 xk and computed its Hessian as the sum of 2n simpler determinants. We obtain the same result directly using Theorem 3. We have f(t) = et and αi = 1 for every i. Hence f ′(t) = f ′′(t) = et. Then Theorem 3 implies that det HF(x) = 1 + g(x) n n −1 eng(x)(−1)n+1(n −1)g(x)n−2 = (−1)n+1 n −1 + n n Y k=1 xk e n n Q k=1 xk n Y k=1 xn−2 k .
Moreover we obtain the inverse of the Hessian matrix.
HF(x)−1 = 1 g(x)eg(x) mat 1 n −1 − 1 (n−1)2 g(x) + n(n −1) −δij xixj = mat 1 e n Q k=1 xk n Q k=1 xk 1 n −1 − n Q k=1 xk (n −1)2 + n(n −1) n Q k=1 xk −δij xixj Example 3 Consider the function F(x) = n s n Q k=1 xk, i.e. the geometric mean.
Using the notation of Theorem 3, we have f(t) = n √ t and αi = 1 for every i.
Hence f ′(t) = 1 nt 1 n −1 and f ′′(t) = 1 n 1 n −1 t 1 n −2. Then Theorem 3 implies that det HF(x) = 1+g(x) 1 n 1 n −1 g(x) 1 n −2 1 ng(x) 1 n −1 n n −1 1 nng(x)1−n(−1)n+1(n−1)g(x)n−2 = 0 .
3 Proofs In our proofs we will need the following two lemmas. We present them also with their short proofs.
Lemma 1 (Matrix determinant lemma) (, Lemma 1.1) Let A be an invert-ible n × n matrix and let u, v ∈Rn be column vectors. Then det(A + uvT) = (1 + vTA−1u) det A .
Proof. By a direct computation we easily obtain the identity A 0 vT 1 I + A−1uvT A−1u 0T 1 I 0 −vT 1 = A u 0T 1 + vTA−1u .
On Hessians of composite functions 8605 Taking determinants of both sides we immediately obtain det(A + uvT) = det A · det(I + A−1uvT) = det A · (1 + vTA−1u) .
□ Lemma 2 (Sherman-Morrison formula) (, Section 2.7.1) Let A be an in-vertible n × n matrix and let u, v ∈Rn be column vectors. Suppose that the matrix A + uvT is invertible. Then (A + uvT)−1 = I − A−1uvT 1 + vTA−1u A−1 .
Proof. From the assumption and Lemma 1 it follows that 1 + vTA−1u ̸= 0.
Then I = I + A−1uvT −A−1uvT + (vTA−1u)A−1uvT 1 + vTA−1u = I + A−1uvT −A−1uvT + A−1u(vTA−1u)vT 1 + vTA−1u = A−1(A + uvT) −A−1uvTA−1 1 + vTA−1u (A + uvT) = A−1 −A−1uvTA−1 1 + vTA−1u (A + uvT) We obtain the result by multiplying by (A + uvT)−1.
□ Using these lemmas we now prove our theorems.
Proof of Theorem 1. The second-order partial derivatives of F are ∂2F ∂xi∂xj = f ′′(g(x)) ∂g ∂xi (x) ∂g ∂xj (x) + f ′(g(x)) ∂2g ∂xi∂xj (x) .
(1) Hence the Hessian matrix can be written as HF(x) = A + uvT, where A = f ′(g(x))Hg(x) , u = f ′′(g(x))∇g(x) , v = ∇g(x) .
(2) From Lemma 1 we obtain det HF(x) = 1+∇g(x)T· f ′(g(x))Hg(x) −1·f ′′(g(x))∇g(x) det f ′(g(x))Hg(x) = 1 + f ′′(g(x)) f ′(g(x)) ∇g(x)T · Hg(x)−1 · ∇g(x) f ′(g(x))n det Hg(x) .
□ 8606 ˇ Cestm´ ır B´ arta, Martin Kol´ aˇ r and Jan ˇ Sustek Proof of Theorem 2. As in the proof of Theorem 1 we obtain (1) and (2).
Then Lemma 2 implies HF(x)−1 = I − f ′(g(x))Hg(x) −1 · f ′′(g(x))∇g(x) · ∇g(x) T 1 + ∇g(x) T · f ′(g(x))Hg(x) −1 · f ′′(g(x))∇g(x) · f ′(g(x))Hg(x) −1 = I − Hg(x)−1 · ∇g(x) · ∇g(x)T f ′(g(x)) f ′′(g(x)) + ∇g(x)T · Hg(x)−1 · ∇g(x) · Hg(x)−1 f ′(g(x)) .
□ Proof of Theorem 3. The derivatives of the function g are ∂g ∂xi = αi xi g(x) , ∂2g ∂x2 i = αi(αi −1) x2 i g(x) , ∂2g ∂xi∂xj = αiαj xixj g(x) .
Therefore its gradient is equal to ∇g(x) = g(x) col αi xi and its Hessian matrix is Hg(x) = mat αiαj xixj −diag αi x2 i g(x) = −g(x)(A + uvT) , where A = diag αi x2 i , u = −col αi xi , v = col αi xi .
Then Lemma 1 implies that det Hg(x) = (−g(x))n 1 −row αi xi · diag x2 i αi · col αi xi n Y k=1 αk x2 k = (−g(x))n(1 −|α|) n Y k=1 αk x2 k = (−1)n(1 −|α|) n Y k=1 αkxnαk−2 k .
(3) Lemma 2 implies that Hg(x)−1 = −1 g(x) diag x2 i αi + diag xi αi · col αi xi · row αi xi · diag x2 i αi 1 −row αi xi · diag x2 i αi · col αi xi !
= −1 g(x) diag x2 i αi + mat xixj 1 −|α| .
(4) On Hessians of composite functions 8607 We will use the following identity row αi xi · diag x2 i αi · col αi xi + row αi xi · mat xixj 1 −|α| · col αi xi = |α| + |α|2 1 −|α| = |α| 1 −|α| .
(5) Then (3), (4), (5) and Theorem 1 imply that det HF(x) = 1 + f ′′(g(x)) f ′(g(x)) g(x) row αi xi · −1 g(x) diag x2 i αi + mat xixj 1 −|α| · g(x) col αi xi × f ′(g(x))n(−1)n(1 −|α|) n Y k=1 αkxnαk−2 k = 1 −g(x)f ′′(g(x)) f ′(g(x)) row αi xi · diag x2 i αi · col αi xi + row αi xi · mat xixj 1 −|α| · col αi xi × f ′(g(x))n(−1)n+1(|α| −1) n Y k=1 αkxnαk−2 k = 1 + g(x)f ′′(g(x)) f ′(g(x)) |α| |α| −1 f ′(g(x))n(−1)n+1(|α| −1) n Y k=1 αkxnαk−2 k .
By a direct computation, using (5), we obtain ∇g(x)T · Hg(x)−1 · ∇g(x) = g(x) row αi xi · −1 g(x) diag x2 i αi + mat xixj 1 −|α| · g(x) col αi xi = −g(x) row αi xi · diag x2 i αi · col αi xi + row αi xi · mat xixj 1 −|α| · col αi xi = g(x) |α| |α| −1 (6) and Hg(x)−1 · ∇g(x) · ∇g(x)T = −1 g(x) diag x2 i αi + mat xixj 1 −|α| · g(x) col αi xi · g(x) row αi xi = −g(x) diag x2 i αi · col αi xi · row αi xi + 1 1 −|α| mat xixj · col αi xi · row αi xi = g(x) |α| −1 mat αjxi xj .
(7) 8608 ˇ Cestm´ ır B´ arta, Martin Kol´ aˇ r and Jan ˇ Sustek Then (6), (7) and Theorem 2 imply HF(x)−1 = I − Hg(x)−1 · ∇g(x) · ∇g(x)T f′(g(x)) f′′(g(x)) + ∇g(x)T · Hg(x)−1 · ∇g(x) !
· Hg(x)−1 f ′(g(x)) = I − g(x) |α|−1 mat αjxi xj f′(g(x)) f′′(g(x)) + g(x) |α| |α|−1 !
· −1 g(x)f ′(g(x)) diag x2 i αi + mat xixj 1 −|α| = 1 g(x)f ′(g(x)) β mat αjxi xj −I · diag x2 i αi + mat xixj 1 −|α| , (8) where β = g(x) |α|−1 f′(g(x)) f′′(g(x)) + g(x) |α| |α|−1 .
Now we have β mat αjxi xj · diag x2 i αi = β mat xixj , (9) β mat αjxi xj · mat xixj 1 −|α| = β|α| 1 −|α| mat xixj , (10) −I · diag x2 i αi = −mat δij αi xixj , (11) −I · mat xixj 1 −|α| = 1 |α| −1 mat xixj .
(12) From the identity β + β|α| 1−|α| = β 1−|α| we obtain that (9) + (10) = −1 f′(g(x)) g(x)f′′(g(x))(|α| −1)2 + |α|(|α| −1) mat xixj .
(13) Finally, (8), (11), (12) and (13) imply that HF(x)−1 = 1 g(x)f ′(g(x)) mat 1 |α| −1− 1 f′(g(x)) g(x)f′′(g(x))(|α| −1)2 + |α|(|α| −1) −δij αi xixj .
□ Acknowledgement The authors were supported by grant GAˇ CR P201/12/2351 of the Czech Sci-ence Foundation and by grant SGS08/Pˇ rF/2014 of the University of Ostrava.
On Hessians of composite functions 8609 References Ch.M. Bishop. Neural networks for pattern recognition. Oxford University Press, 1995.
B.-Y. Chen. An Explicit Formula of Hessian Determinants of Composite Functions and Its Applications. Kragujevac Journal of Mathematics, 36 (1), 2012, 27–39.
J. Ding, A. Zhou. Applied Mathematics Letters, 20 (12), 2007, 1223–1226.
J. Milnor. Morse theory. Princeton University Press, 1969.
W.H. Press, S.A. Teukolsky, W.T. Vetterling, B.P. Flannery. Numerical Recipes: The Art of Scientific Computing (3rd ed.), Cambridge University Press, New York, 2007.
P. Trojovsk´ y, E. Hlad´ ıkov´ a. On the Hessian of the Exponential Function with n Variables. International Journal of Pure and Applied Mathematics, 66 (3), 2011, 287–296.
Received: October 19, 2014; Published: December 1, 2014 |
15110 | https://www.sigmaaldrich.com/US/en/product/sigald/161527?srsltid=AfmBOop9zRC1VfAVz1YK6yFH1WfF6sAsqZTEvj5SJmkjPiUF7Xw6DjE4 | Sodium hydrosulfide 207683-19-0
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Sodium hydrosulfide hydrate
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About This Item
Linear Formula:
NaSH·xH 2 O
CAS Number:
207683-19-0
Molecular Weight:
56.06 (anhydrous basis)
MDL number:
MFCD00149796
UNSPSC Code:
12352302
PubChem Substance ID:
329751132
NACRES:
NA.55
Form:
chips
flakes
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Properties
form
chips
flakes
Quality Level
100
concentration
≥60% (by Na 2 S 2 O 3, titration)
mp
52-54°C (lit.)
SMILES string
[Na]S.[H]O[H]
InChI
1S/Na.H2O.H2S/h;21H2/q+1;;/p-1
InChI key
ZNKXTIAQRUWLRL-UHFFFAOYSA-M
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| ###### This Item | 157953 | 27029 | 464422 |
--- --- |
| Sigma-Aldrich 161527 Sodium hydrosulfide hydrate Quick View | Sigma-Aldrich 157953 Sodium hydrosulfite Quick View | Sigma-Aldrich 27029 Sodium cholate hydrate Quick View | Sigma-Aldrich 464422 2-Ketobutyric acid sodium salt hydrate Quick View |
| form chips, flakes | form powder | form powder | form powder |
| Quality Level 100 | Quality Level 200 | Quality Level 200 | Quality Level 100 |
| mp 52-54°C (lit.) | mp - | mp - | mp 210°C (dec.) (lit.) |
| concentration ≥60% (by Na 2 S 2 O 3, titration) | concentration - | concentration - | concentration - |
Description
General description
Sodium hydrosulfide hydrate is a hydrated inorganic salt of sodium. It participates in the synthesis of (E)-2-cyano-2-(thiazolidin-2-ylidene)ethanethioamide.
Application
It may be used as a sulfur nucleophile to induce the C-S bond formation in α,β-dichloro vinyl ketones to form 5- to 8-membered cyclic thioethers.
Sodium hydrosulfide hydrate may be used in the synthesis of following:
benzothiazole
4-methoxybenzothioamide
2-(4-methoxyphenyl)imidazoline
7-chloro-4′-methoxythioflavone
Safety Information
Pictograms
GHS06,GHS05,GHS09
Signal Word
Danger
Hazard Statements
H301,H314,H400
Precautionary Statements
P260 - P273 - P280 - P301 + P310 + P330 - P303 + P361 + P353 - P305 + P351 + P338
Hazard Classifications
Acute Tox. 3 Oral - Aquatic Acute 1 - Skin Corr. 1B
Storage Class Code
6.1D - Non-combustible acute toxic Cat.3 / toxic hazardous materials or hazardous materials causing chronic effects
WGK
WGK 3
Flash Point(F)
194.0 °F - closed cup
Flash Point(C)
90 °C - closed cup
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SHBR6131
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15111 | https://www.revivetherapeuticservices.com/does-weather-affect-your-modd-the-science-behind-weather-and-mood | Does Weather Affect Your Mood--The Science Behind Weather and Mood
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Does Weather Affect Your Mood--The Science Behind Weather and Mood
Revive Therapeutic Services
Jan 21
3 min read
Updated: Feb 4
As spring approaches and daylight stretches longer into the evening, many of us begin to notice a shift—not just in the seasons, but in our moods. The warm breeze, blossoming flowers, and extended sunlight bring a renewed sense of energy and positivity. But why does this happen? How exactly does weather—and specifically daylight—affect our mood? In this blog, we’ll explore the fascinating connection between weather, daylight, and our mood, and answer the question: does weather affect mood?
The Science Behind Weather Affecting Mood
For centuries, people have believed in the profound impact weather has on emotions. Modern science confirms this, with numerous studies revealing the intricate link between environmental factors like sunlight, temperature, and even humidity, and our mental health. One of the most significant influences is daylight, which plays a crucial role in regulating our circadian rhythms—the natural 24-hour cycles that govern sleep, energy levels, and mood.
When we experience more daylight, our brains produce less melatonin, a hormone that induces sleepiness, and more serotonin, often referred to as the “happiness hormone.” This biochemical shift explains why longer days in spring and summer often lead to improved mood, increased energy, and a greater sense of well-being.
Seasonal Affective Disorder (SAD)
On the flip side, the lack of daylight during winter months can lead to Seasonal Affective Disorder (SAD), a form of depression that affects millions of people worldwide. Symptoms of SAD include low energy, difficulty concentrating, and feelings of sadness or hopelessness. As spring approaches and daylight hours increase, many individuals with SAD notice a significant improvement in their symptoms, underscoring the powerful relationship between sunlight and mental health.
The Role of Weather in Affecting Our Mood
While daylight is a key factor, other weather elements can also influence mood. Warm, sunny days are often associated with feelings of happiness and relaxation, while gloomy, rainy days might evoke sadness or introspection. Interestingly, moderate temperatures have been linked to higher productivity and creativity, suggesting that weather’s impact extends beyond just mood.
However, it’s important to note that individual responses to weather can vary. While some people thrive in the heat of summer, others feel their best during cooler autumn days. Personal preferences, lifestyle, and even cultural factors can shape how weather affects each person’s mood.
Daylight and Its Impact on Mental Health
One of the most striking effects of increased daylight is its ability to combat symptoms of depression and anxiety. Exposure to natural light has been shown to:
Boost Vitamin D Levels:Sunlight helps our bodies produce Vitamin D, which is essential for bone health and has been linked to improved mood.
Improve Sleep Quality:By regulating melatonin production, daylight helps align our sleep-wake cycles, leading to more restful sleep.
Enhance Cognitive Function:Studies suggest that exposure to natural light can improve focus, memory, and overall cognitive performance.
For those who spend most of their time indoors, incorporating more natural light into daily routines can make a noticeable difference. Whether it’s taking a walk during lunch or working near a window, these small changes can help harness the mood-enhancing benefits of daylight.
Tips for Embracing Spring and Its Mood-Boosting Benefits
As we welcome the arrival of spring, there are several ways to make the most of the season’s longer days and better weather:
Spend Time Outdoors:Engage in activities like hiking, gardening, or simply enjoying a picnic in the park to soak up natural light.
Exercise Regularly:Physical activity releases endorphins, which complement the mood-enhancing effects of daylight.
Practice Mindfulness:Take a moment to appreciate the beauty of spring, whether it’s listening to birdsong, admiring blooming flowers, or feeling the warmth of the sun.
Maintain a Balanced Routine:Align your daily schedule with natural light patterns by waking up earlier and winding down as the sun sets.
Does Weather Affect Mood? Absolutely!
In conclusion, the arrival of spring and the lengthening daylight hours offer a natural remedy for winter blues. Weather, and particularly daylight, undeniably influences mood, affecting everything from energy levels to mental health. By understanding and embracing this connection, we can take proactive steps to harness the positive effects of longer days and warmer weather.
So as the season changes, step outside, feel the sun on your skin, and let the vibrant energy of spring elevate your mood. And remember, whether it’s a sunny afternoon or a cool, breezy morning, each moment spent in nature can contribute to a happier, healthier you.
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15112 | http://hyperphysics.phy-astr.gsu.edu/hbase/Particles/neutrino.html | | | | | | | | | | | |
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| Electron Neutrinos and Antineutrinos The history of a particle that appeared to have no charge and no mass is an interesting one. The electron neutrino (a lepton) was first postulated in 1930 by Wolfgang Pauli to explain why the electrons in beta decay were not emitted with the full reaction energy of the nuclear transition. The apparent violation of conservation of energy and momentum was most easily avoided by postulating another particle. Enrico Fermi called the particle a neutrino and developed a theory of beta decay based on it, but it was not experimentally observed until 1956. This elusive particle, with no charge and almost no mass, could penetrate vast thicknesses of material without interaction. The mean free path of a neutrino in water would be on the order of 10x the distance from the Earth to the Sun. In the standard Big Bang model, the neutrinos left over from the creation of the universe are the most abundant particles in the universe. This remnant neutrino density is put at 100 per cubic centimeter at an effective temperature of 2K (Simpson). The background temperature for neutrinos is lower than that for the microwave background (2.7K) because the neutrino transparency point came earlier. The sun emits vast numbers of neutrinos which can pass through the earth with little or no interaction. This leads to the statement "Solar neutrinos shine down on us during the day, and shine up on us during the night!". Bahcall's modeling of the solar neutrino flux led to the prediction of about 5 x 106 neutrinos/cm2s. A remarkable opportunity for observing neutrinos came with Supernova 1987A when the Japanese observing team detected neutrinos almost coincident with the discovery of the light from the supernova. Neutrinos interact only by the weak interaction. Their interactions are usually represented in terms of Feynman diagrams. | | | | --- | Neutrinos as leptons | Role in supernova | Other neutrino types | | | | --- | | Detection of neutrinos | Does the neutrino have any mass? | | | | Why do we say that neutrinos are left-handed? | | | | Neutrino cross-section for interaction | | | | Neutrinos in the early universe | | Index References Kearns, et al. Simpson Bahcall |
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| Detection of Neutrinos The first experimental observation of the neutrino interacting with matter was made by Frederick Reines, Clyde Cowan, Jr, and collaborators in 1956 at the Savannah River Plant in South Carolina. Their neutrino source was a nuclear reactor (it actually produced antineutrinos from beta decay). | | | --- | | | Modern neutrino detectors at IMB in Ohio and Kamiokande in Japan detected neutrinos from Supernova 1987A. A new neutrino detector at Sudbury, Ontario began collecting data in October of 1999. Another Japanese neutrino detector called Super Kamiokande became operational in April 1996. | An early set of experiments with a facility called the solar neutrino telescope, measured the rate of neutrino emission from the sun at only one third of the expected flux. Often referred to as the Solar Neutrino Problem, this deficiency of neutrinos has been difficult to explain. Recent results from the Sudbury Neutrino Observatory suggest that a fraction of the electron neutrinos produced by the sun are transformed into muon neutrinos on the way to the earth. The observations at Sudbury are consistent with the solar models of neutrino flux assuming that this "neutrino oscillation" is responsible for observation of neutrinos other than electron neutrinos. | | | Cherenkov Radiation | | Index Reference McDonald, Klein & Wark |
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| Sudbury Neutrino Observatory The new Sudbury Neutrino Observatory (SNO) consists of a 1000 metric ton bottle of heavy water suspended in a larger tank of light water. The apparatus is located in Sudbury, Ontario, Canada at a depth of about 2 km down in a nickel mine. A 18 m diameter geodesic array of 9,500 photomultiplier tubes surrounds the heavy water to detect Cerenkov radiation from the neutrino interaction which dissociates deuterium: | | | | --- | | | | | Show other detection reactions for SNO | | The distinctive characteristic of the heavy water observatory is that it can measure both the electron neutrino flux and the total neutrino flux (electron, muon and tau neutrinos). It should allow them to determine whether neutrinos change flavors. If so, it could explain the solar neutrino problem and would show that the neutrinos have mass. SNO began operating in production mode in October, 1999, and as of Summer 2000 had collected a sizable number of neutrino events both from the sun (the main focus of the experiment) and from atmospheric events with pions and muons. The Cerenkov cones of the solar neutrinos center about the direction opposite the sun, showing about the same flux at night as during the day. This was an expected result, since the mean free path of a neutrino in matter is about 22 lightyears in lead and having the earth in the path makes little difference. A sizable number of the atmospheric neutrino events come from below, having traveled all the way through the earth and forming the Cerenkov cone in the photomultiplier tubes at the top of the spherical heavy-water ball. These Cerenkov cones are scattered all around the sphere, while the solar ones of course show a precise anti-solar direction. The depth of the detector protects it from the intense bombardment of cosmic ray muons which reaches the earth's surface. The detector measures only about 70 muon events per day, and they are easily distinguished from neutrino events since the muon interacts by the electromagnetic interaction and produces a much larger signal in the detector array. In order to detect the ring of light which is the signature of Cerenkov radiation, the responses of all the photomultiplier tubes (PMTs) are monitored with a very short time scale. In order to be counted as an "event" in the detector, at least 20 PMTs must be triggered within an interval of 100 nanoseconds. | | | How SNO detects neutrinos | | Index Reference Feder Simpson McDonald, Klein & Wark |
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| The Solar Neutrino Telescope Raymond Davis of Brookhaven National Laboratory constructed a neutrino detector 1.6 km underground in the Homestake Gold Mine in Lead, South Dakota. The detector consists of a 378,000 liter tank of perchloroethylene, which is further isolated by being submerged in water. Theoretical expections were about one neutrino-chlorine interaction per day, but the measured solar neutrino events were about a third of that, raising serious questions about the abundance of solar neutrinos (the Solar Neutrino Problem). The detection of neutrinos by this instrument was based on the interaction of neutrinos with chlorine nuclei to produce argon. The argon can be removed from the tank and measured so that the number of neutrinos captured in a given time interval can be determined. The argon decays back to the chlorine isotope from which it was created by the process of electron capture. The detection of this transition is aided by the definite energy of the x-ray emitted during the electron capture process. This mine experiment was able to detect about 15 argon atoms a month, according to Simpson. | | | --- | | | Perchloroethylene is ordinary dry-cleaning fluid, but 400,000 gallons is a lot of cleaning fluid. Davis denies the story that he was besieged by wire coat-hanger salesmen after the large purchase. | | Index Reference Simpson |
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| Detection of Supernova Neutrinos Since the neutrino can pass through the entire Earth without interaction, it takes specialized techniques to detect one. After being postulated by Pauli in 1930 to explain anomalies in beta decay, they were not actually detected until 1956 by Reines and Cowan. Detection of neutrinos is now well developed and a classic opportunity for neutrino detection occurred with Supernova 1987A. A burst of ten neutrinos was detected within a time interval of about 15 seconds at a neutrino detector deep in a mine in Japan. They had to penetrate the Earth to get to the detector. | | | --- | | | More detail Energies in eV | | Index |
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| Neutrino Mass? No definite mass has been measured for the neutrino, and the standard comment about most experiments is "the results are consistent with zero mass for the neutrino". But this raises certain theoretical problems and there have been many attempts to set a range for the mass of the neutrino. Since its mass is evidently very small, if non-zero, the mass is usually stated in terms of its energy equivalent in electron volts. Most experiments conclude that the mass equivalent of the neutrino is less than 50 eV. One of the recent pieces of information about neutrino mass came from the neutrinos observed from Supernova 1987A. Ten neutrinos arrived within 15 seconds of each other after traveling 180,000 light years, and they differed by a up to factor of three in energy. This limits the neutrino rest mass energy to less than about 30 eV (Rohlf). New experimental evidence from the Super-Kamiokande neutrino detector in Japan represents the strongest evidence to date that the mass of the neutrino is non-zero. Models of atmospheric cosmic ray interactions suggest twice as many muon neutrinos as electron neutrinos, but the measured ratio was only 1.3:1. The interpretation of the data suggested a mass difference between electron and muon neutrinos of 0.03 to 0.1 eV. Presuming that the muon neutrino would be much more massive than the electron neutrino, then this implies a muon neutrino mass upper bound of about 0.1 eV. The recent neutrino measurements at the Sudbury Neutrino Observatory are consistent with the modeled total neutrino flux and add evidence for neutrino oscillation, a process which can only occur if the neutrinos have mass. | Index References Rohlf Kearns, et al. |
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| Some Neutrino History The electron neutrino (a lepton) was first postulated in 1930 by Wolfgang Pauli to explain why the electrons in beta decay were not emitted with the full reaction energy of the nuclear transition. The apparent violation of conservation of energy and momentum was most easily avoided by postulating another particle. Enrico Fermi called the particle a neutrino and developed a theory of beta decay based on it, but it was not experimentally observed until 1956. Wolfgang Pauli introduced the neutrino to the world of physics in 1930 with a famous letter to "Liebe Radioacktive Damen und Herren" (Dear radioactive ladies and gentlemen) at the Tubingen meeting of radioactivity researchers. Pauli's first public discussion of the neutrino was at the 7th Solvay Conference in Brussels in 1933. References: Wolfgang Pauli and Modern Physics Wiki on Wolfgang Pauli | Index References Rohlf Kearns, et al. |
| | | | --- | | HyperPhysics Quantum Physics | R Nave | | Go Back | |
15113 | https://emorysurgicalfocus.com/2020/10/23/afferent-loop-syndrome/ | Afferent loop syndrome | Surgical Focus
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Afferent loop syndrome
Posted on October 23, 2020 by E. Lawson
Termsinsuk P, Chantarojanasiri T, Pausawasdi N. Diagnosis and treatment of the afferent loop syndrome.Clin J Gastroenterol. 2020 Oct;13(5):660-668.
“ALS is a rare condition with the incidence ranging from 0.2 to 1.0% depending on the type of operation and anastomotic limb reconstruction. ALS has been reported in 0.3–1.0% of patients after total gastrectomy with Billroth II or Roux-en-Y reconstruction, 1% after laparoscopic distal gastrectomy with Billroth II reconstruction, and 0.2% after distal gastrectomy with Roux-en-Y reconstruction [4–6]. Other operations of which ALS can occur include total gastrectomy with loop esophagojejunostomy with simple or pouch Roux-en-Y reconstruction and pancreaticoduodenectomy with conventional loop and Roux-en-Y reconstruction; nonetheless, the data on incidence were limited .”
Dumon K and Dempsey DT. (2019). Postgastrectomy Syndromes. In Charles J Yeo (Ed.) Shackelford’s Surgery of the Alimentary Tract, 8th ed.: 719-734. Elsevier, Philadelphia.
Full-text for Emory users.
“Afferent loop obstruction, also called afferent loop syndrome, is a mechanical complication that infrequently occurs following construction of a GJ. The creation of a GJ leaves a segment of proximal small bowel (duodenum and proximal jejunum) upstream from the anastomosis. With Billroth II or loop GJ the afferent limb conducts bile, pancreatic juices, and other proximal intestinal secretions toward the GJ 51 ; with Roux-en-Y the afferent limb conducts the succus toward the jejunojejunostomy and is also called the biliopancreatic limb. The operations most commonly associated with afferent loop obstruction are Billroth II and Roux-en-Y GJ (distal gastrectomy or gastric bypass), and Roux-en-Y esophagojejunostomy (total gastrectomy). 52 The incidence of significant afferent loop obstruction after these procedures is low (0.3% to 1.0%) and is similar after open and laparoscopic surgery.”
FIGURE 62.7.Causes of afferent loop syndrome include (A) kinking and angulation of the afferent limb, (B) internal herniation of the afferent limb behind the efferent limb, (C) stenosis of the gastrojejunal anastomosis, (D) redundancy of the afferent limb leading to volvulus, or (E) adhesions involving the afferent limb. (Modified from Miller TA, Mercer DW. Derangements in gastric function secondary to previous surgery. In: Miller TA, ed.Modern Surgical Care: Physiologic Foundations and Clinical Applications.2nd ed. St. Louis: Quality Medical; 1998:402.)
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15114 | https://pmc.ncbi.nlm.nih.gov/articles/PMC5944396/ | Gender Dysphoria in Adults: An Overview and Primer for Psychiatrists - PMC
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Gender Dysphoria in Adults: An Overview and Primer for Psychiatrists
William Byne
William Byne
1 Mental Illness Research Education and Clinical Center, James J Peters VA Medical Center, Bronx, New York.
2 Department of Psychiatry, Icahn School of Medicine at Mount Sinai and Center for Transgender Medicine and Surgery at Mount Sinai, New York, New York.
Find articles by William Byne
1,,2,,, Dan H Karasic
Dan H Karasic
3 Department of Psychiatry, University of California, San Francisco, San Francisco, California.
Find articles by Dan H Karasic
3, Eli Coleman
Eli Coleman
4 Program in Human Sexuality, Department of Family Medicine and Community Health, University of Minnesota Medical School, Minneapolis, Minnesota.
Find articles by Eli Coleman
4, A Evan Eyler
A Evan Eyler
5 Departments of Psychiatry and Family Medicine, University of Vermont College of Medicine, Burlington, Vermont.
Find articles by A Evan Eyler
5, Jeremy D Kidd
Jeremy D Kidd
6 Department of Psychiatry, Division on Substance Use Disorders, College of Physicians and Surgeons of Columbia University, New York, New York.
Find articles by Jeremy D Kidd
6, Heino FL Meyer-Bahlburg
Heino FL Meyer-Bahlburg
7 Division of Gender, Sexuality, and Health, New York State Psychiatric Institute/Department of Psychiatry, College of Physicians and Surgeons of Columbia University, New York, New York.
Find articles by Heino FL Meyer-Bahlburg
7, Richard R Pleak
Richard R Pleak
8 Department of Psychiatry, Division of Child and Adolescent Psychiatry, Hofstra North Shore-LIJ School of Medicine, Albert Einstein College of Medicine, Zucker Hillside Hospital, Ambulatory Care Pavilion, Glen Oaks, New York.
Find articles by Richard R Pleak
8, Jack Pula
Jack Pula
9 Department of Psychiatry, Division of Gender, Sexuality and Health, College of Physicians and Surgeons of Columbia University, New York, New York.
Find articles by Jack Pula
9
Author information
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Copyright and License information
1 Mental Illness Research Education and Clinical Center, James J Peters VA Medical Center, Bronx, New York.
2 Department of Psychiatry, Icahn School of Medicine at Mount Sinai and Center for Transgender Medicine and Surgery at Mount Sinai, New York, New York.
3 Department of Psychiatry, University of California, San Francisco, San Francisco, California.
4 Program in Human Sexuality, Department of Family Medicine and Community Health, University of Minnesota Medical School, Minneapolis, Minnesota.
5 Departments of Psychiatry and Family Medicine, University of Vermont College of Medicine, Burlington, Vermont.
6 Department of Psychiatry, Division on Substance Use Disorders, College of Physicians and Surgeons of Columbia University, New York, New York.
7 Division of Gender, Sexuality, and Health, New York State Psychiatric Institute/Department of Psychiatry, College of Physicians and Surgeons of Columbia University, New York, New York.
8 Department of Psychiatry, Division of Child and Adolescent Psychiatry, Hofstra North Shore-LIJ School of Medicine, Albert Einstein College of Medicine, Zucker Hillside Hospital, Ambulatory Care Pavilion, Glen Oaks, New York.
9 Department of Psychiatry, Division of Gender, Sexuality and Health, College of Physicians and Surgeons of Columbia University, New York, New York.
Address correspondence to: William Byne, MD, PhD, James J. Peters VA Medical Center, Research Bldg, Rm 5F-04B, Bronx, NY 10468 william.byne@mssm.edu
This report was prepared by the American Psychiatric Association (APA) Workgroup on Gender Dysphoria with oversight by the APA Council on Quality Care. This article has been extracted and revised from a larger document, “Gender Dysphoria and Gender-variant Patients: A Primer for Psychiatrists,” which was approved by the APA Board of Trustees as an APA Resource Document. A course based on this content was also presented as APA Course 315, Transgender and Intersex for the Practicing Psychiatrist, given at the 168th Annual Meeting of the APA, May 16, 2015, Toronto, Canada, and Course 4196 by the same name given at the 169th Annual Meeting of the APA, May 24, 2016, Atlanta, GA.
Collection date 2018.
© William Byne et al. 2018; Published by Mary Ann Liebert, Inc.
This Open Access article is distributed under the terms of the Creative Commons License ( which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
PMC Copyright notice
PMCID: PMC5944396 PMID: 29756044
Abstract
Regardless of their area of specialization, adult psychiatrists are likely to encounter gender-variant patients; however, medical school curricula and psychiatric residency training programs devote little attention to their care. This article aims to assist adult psychiatrists who are not gender specialists in the delivery of respectful, clinically competent, and culturally attuned care to gender-variant patients, including those who identify as transgender or transsexual or meet criteria for the diagnosis of Gender Dysphoria (GD) as defined by The Diagnostic and Statistical Manual of Mental Disorders (5th edition). The article will also be helpful for other mental health professionals. The following areas are addressed: evolution of diagnostic nosology, epidemiology, gender development, and mental health assessment, differential diagnosis, treatment, and referral for gender-affirming somatic treatments of adults with GD.
Keywords: assessment, gender dysphoria, gender transition, mental health, psychiatry, intersex, transgender
Introduction
Individuals who would likely be considered transgender today are evident throughout the historical record.1 The historical and sociocultural conceptualizations of gender variance, and their evolution within mental health professions over the past century and a half are reviewed elsewhere.2
Nineteenth and 20th century theories of gender variance and views of appropriate treatment were pathologizing and highly stigmatizing to transgender people.2 While mainstream psychiatry is now more affirming of gender variance, transgender individuals often are aware of the history in this area and many are likely to have encountered providers who adhere to outdated stigmatizing theories and approaches to treatment.3 Today's mental health professionals should, therefore, be familiar with the history in this area as it is not unusual for gender-variant patients to have apprehensions about seeking mental healthcare or to raise questions about their providers' views and approach to treatment considering that history.
Between 1963 and 1979, over 20 university-based gender identity clinics opened in the United States.2,4 These clinics provided interdisciplinary care that included psychiatrists and other mental health professionals and played an important role in the provision of medical services to transgender people and in promoting research to improve their care.2,4 The majority of these clinics closed following a 1981 decision of the U.S. Department of Health and Human Services (HHS) that labeled sex reassignment surgery as experimental,5 a decision what was overturned by HHS in 2014 in a determination that concluded that the 1981 decision was “unreasonable and contrary to contemporary science and medical standards of care.”6
With the closure of the academic gender clinics, transgender people in the United States came to rely on a loose network of medical and mental health providers, often affiliated with the Harry Benjamin International Gender Dysphoria Association (HBIGDA), which was subsequently renamed the World Professional Association for Transgender Health (WPATH). HBIGDA/WPATH developed and successively revised standards of care (SOC) for gender transition, which are currently in their seventh revision as the WPATH SOC7.7 In the WPATH SOC7, mental health professionals are tasked with determining whether those interested in gender-affirming treatments meet eligibility criteria, have capacity for informed consent, and have adequately anticipated the psychosocial impacts of their transition.
The WPATH SOC also provide clinical guidance for health professionals to assist transgender people in their search for psychological well-being in their gendered selves. In the absence of other comprehensive English language guidelines, U.S. providers and their professional associations came to rely heavily on the HBIDGA/WPATH SOC.8–10 Similarly, insurance carriers and tax courts employ WPATH SOC criteria in evaluating the medical necessity of transition treatments for determination of reimbursable and tax-deductible medical expenses.11–14
With transition services offered outside of university-based clinics, U.S. medical schools and residency training programs offered little exposure to the provision of transition services, leaving psychiatrists and other physicians poorly prepared for the growth in demand for these services seen in recent years.15 This article aims to assist adult psychiatrists and other mental health professionals who are not gender specialists in the care of these individuals. Detailed information on the assessment and treatment of gender dysphoria in children and adolescents can be found elsewhere.16–19
A glossary of transgender-related terms is found in Table 1. Providers should be respectful of their patients' identity labels; however, due to the rapid evolution of gender terminology, they may need to clarify how both their patients and colleagues employ particular terms.
Table 1.
Glossary
Assigned gender: the initial gender attributed to an individual after birth; for most individuals, this corresponds to the sex on their original birth certificate, aka assigned gender, birth sex.
Cisgender: a term for individuals whose experienced and expressed gender are congruent with their gender assigned at birth, that is, those who are not transgender.
Experienced gender: one's sense of belonging or not belonging to a particular gender, aka gender identity.
Expressed gender: how one expresses one's experienced gender.
Gender: a person's social status as male (boy/man) or female (girl/woman), or alternative category.
Gender-affirming surgery: surgical procedures intended to alter a person's body to affirm their experienced gender identity, aka sex reassignment surgery, gender reassignment surgery, and gender-confirming surgery.
Gender assignment: assignment of a gender to an individual. In typically developed newborns, the initial gender assignment (aka “birth-assigned gender”) is usually made on the basis of the appearance of the external genitalia.
Gender binary: a gender-categorization system limited to the two options, male and female. Individuals who identify outside the gender binary may use a variety of gender identity labels, including genderqueer or nonbinary.
Gender dysphoria (not capitalized): distress caused by the discrepancy between one's experienced/expressed gender and one's assigned gender and/or primary or secondary sex characteristics.
Gender Dysphoria (GD) (capitalized): a diagnostic category in DSM-5, with specific diagnoses defined by age group-specific sets of criteria. This article addresses only GD in adults.
Gender identity: one's identity as belonging or not belonging to a particular gender, whether male, female, or a nonbinary alternative, aka experienced gender.
Gender Identity Disorder (GID) a diagnostic category in DSM-III and DSM-IV that was replaced in DSM-5 by GD.
Gender incongruence (not capitalized): incongruence between experienced/expressed gender and assigned gender, and/or psychical gender characteristics.
Gender Incongruence (capitalized): a diagnostic category (analogous to GD in DSM-5) proposed for ICD-11.
Gender role: cultural/societal definition of the roles of males and females (or of alternative genders).
Gender transition: the process through which individuals alter their gender expression and/or sex characteristics to align with their sense of gender identity.
Gender variance: any variation of experienced or expressed gender from socially ascribed norms within the gender binary.
Gendered behavior: behavior in which males and females differ on average.
Genderqueer: an identity label used by some individuals whose experienced and/or expressed gender does/do not conform to the male/female binary or who reject the gender binary.
Intersex conditions: a subset of the somatic conditions known as “disorders of sex development” or “differences of sex development “in which chromosomal sex is inconsistent with genital sex, or in which the genital or gonadal sex is not classifiable as either male or female. Some individuals who report their identity as “intersex” do not have a verifiable intersex condition.
Sex: a person's categorization as biologically male or female, usually on the basis of the genitals and reproductive tract.
Sex assigned at birth: the sex or gender first assigned to an individual after birth. Also known as “natal gender,” “birth-assigned sex,” and “gender assigned at birth.” Often queried as “What sex was listed on your original birth certificate?”
Sexual orientation: a person's pattern of sexual attraction and physiological arousal to others of the same, other, both, or neither sex. Sexual orientation cannot be inferred from one's gender identity. As a show of respect, we recommend that the sexual orientation of transgender individuals be expressed in relation to their gender identity rather than their gender assigned at birth; however, all gender scholars do not follow that convention. Ambiguity in charting can be avoided by using terms such as sexually attracted to men, women, both, or neither.
Transgender: an umbrella term usually referring to persons whose experienced or expressed gender does not conform to normative social expectations based on the gender they were assigned at birth.
Transsexual: a term often reserved for the subset of transgender individuals who desire to modify, or have modified, their bodies through hormones or surgery to be more congruent with their experienced gender.
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On official documents such as birth certificates, driver's licenses, and passports, the traditional category “sex” is equivalent to “gender” in current psychological terminology.
“Trans” (also “Trans”) More recent umbrella terms being increasingly used to avoid distinguishing between transgender and transsexual individuals.
DSM, Diagnostic and Statistical Manual of Mental Disorders; GD, Gender Dysphoria; GID, Gender Identity Disorder; ICD, International Classification of Diseases.
Diagnostic and Statistical Manual of Mental Disorders and Transgender-Related Nosology
The first two editions of the Diagnostic and Statistical Manual of Mental Disorders (DSM) published in 1952 and 1968, respectively, did not include any gender diagnosis.20 The diagnosis, “Transsexualism” (sic), first appeared in 1975 in the ninth revision of the International Classification of Diseases (ICD)-921 and subsequently, in the DSM-III in 1980 under the parent category, Sexual Deviations.22 The defining characteristics of this diagnosis were as follows: (1) discomfort about one's assigned sex; (2) “cross-dressing,” in reality or fantasy, as the other sex, but not for the purpose of sexual excitement; and (3) the desire to get rid of one's primary and secondary sex characteristics and to acquire those of the other sex. DSM-III also included “Gender Identity Disorder of Childhood” (GIDC).
Both transsexualism and GIDC were carried over into DSM-IIIR, but were no longer categorized as sexual deviations. Instead, they were placed within the parent category, Disorders Usually First Evident in Infancy, Childhood, or Adolescence.23 This category also included disruptive behavior disorder, eating disorders, and tic disorders. Under this parent category, DSM-IIIR added a new diagnosis, Gender Identity Disorder of Adolescence and Adulthood Nontranssexual Type (GIDAANT). These changes recognized that gender identity disorder (GID) often begins in childhood, may or may not persist into adolescence and adulthood, and when it does persist, it may not entail a desire for the primary or secondary sexual characteristics of the other sex.
With DSM-IV, the diagnoses of Transsexualism and GIDAANT were discontinued, but GIDC and GIDAA were retained and placed under a new parent category, Sexual and Gender Identity Disorders, a category that also included the unrelated sexual dysfunctions and paraphilias.24 Individuals with somatic intersex conditions, who experienced dysphoria attributable to dissatisfaction with their gender assigned at birth, could be diagnosed with Gender Identity Disorder Not Otherwise Specified.
Retention of the diagnosis by the DSM and its new name, including the word “disorder,” was perceived by many as stigmatizing and contributing to societal discrimination against transgender individuals.25 By analogy to homosexuality, much of the distress and functional impairment associated with being transgender, and required for the diagnosis of GID, could derive from social stigmatization rather than from being transgender, per se. On the other hand, removal of a coded diagnosis for medical classification and billing purposes would limit access to transition care, deny the full impact of gender dysphoria, and prove harmful to transgender individuals.2,26
Ultimately, the diagnosis was retained by DSM-5,27 but its name was changed to Gender Dysphoria (GD), simultaneously removing the stigmatizing “disorder” from its name and shifting the focus to dysphoria as the target symptom for intervention and treatment, rather than gender identity itself.27,28 GD was also moved out of the parent category that included sexual dysfunctions and paraphilias, with which it has nothing in common, and into a separate parent category, also named Gender Dysphoria.
Use of the diagnostic label, GD, requires that a person meets the full criteria specified in DSM-5. This is distinctly different from the historical generic use of the term, gender dysphoria, which refers to the distress caused by a discrepancy between one's experienced gender and assigned gender, whether or not full DSM criteria for GD are met. For clarity here, references to the diagnosis will be capitalized or abbreviated (i.e., Gender Dysphoria or GD) while references to the symptom will not be capitalized or abbreviated (i.e., gender dysphoria).
The DSM is a manual on mental disorders and, therefore, despite the name change, GD retains its classification as a mental disorder. In contrast, the ICD is not limited to only mental disorders. In its forthcoming eleventh iteration, ICD-11, the diagnosis of Gender Incongruence (GI) (corresponding to GD in DSM-5 terminology) will most likely be moved out of the section on mental disorders. Instead, it has been proposed to place it in a separate section tentatively named Conditions Related to Sexual Health or Sexual and Gender Health.29 Placing GI in this section will declassify it as a mental disorder, while maintaining a diagnosis that will facilitate access to care through third party reimbursement, and could eventually lead to American Psychiatric Association (APA) removing GD from the DSM.
Importantly, the GD diagnosis does not apply automatically to people who identify as transgender but is given only to those who either exhibit clinically significant distress or impairment associated with a perceived incongruence between their experienced/expressed gender and their assigned gender or who, after transition, no longer meet full criteria, but require ongoing care (e.g., hormonal replacement therapy). In DSM-5, this latter group is given a “post-transition” specifier.
Unlike previous versions of the DSM, in DSM-5, gender-dysphoric individuals with somatic intersex conditions, who were previously excluded from the diagnosis, can now receive the diagnosis with a specifier to indicate the presence of the intersex condition. DSM-5 is also the first DSM to recognize the legitimacy of gender identities outside the gender binary such that individuals with GD are no longer described as identifying simply as “the other gender,” but as “the other gender (or some alternative gender different from one's assigned gender).” Examples of alternative genders include eunuch, genderqueer, and nonbinary.
Epidemiology
Epidemiological research has employed different measures of transgender populations, resulting in varying estimates of prevalence.30,31 Some studies assessed the fraction of a population, which had received the DSM-IV diagnosis of GID or the ICD 10 diagnosis of transsexualism, both of which were limited to clinical populations who sought binary transition (male-to-female or female-to-male). For example, the prevalences reported in DSM-5 (0.005–0.014% for birth-assigned males; 0.002–0.003% for birth-assigned females) are based on people who received a diagnosis of GID or transsexualism, and were seeking hormone treatment and surgery from gender specialty clinics,25 and, therefore, do not reflect the prevalence of all individuals with gender dysphoria or who identify as transgender.
The prevalence of transgender people receiving gender specialty care in the Netherlands has been estimated at 0.008% for transgender women and 0.003% for transgender men.32 More recent data for those obtaining surgery in Belgium were similar.33 In Sweden, point prevalence in 2010 was estimated to be 0.013% for transgender women and 0.008% for transgender men.34 A higher percentage, 0.023%, received a diagnosis of GID recorded in the health records of the U.S. Veteran's Administration.35
Other studies, rather than measuring the proportion of a population that received a clinical diagnosis, have reported on those who self-identified as transgender or gender incongruent, and found that measuring self-identity yields much higher numbers. In 2016, data from the Center for Disease Control's Behavioral Risk Factor Surveillance System suggested that 0.6% of U.S. adults identify as transgender, double the estimate utilizing data from the previous decade.36
In a large Massachusetts population-based phone survey, 0.5% of the population (age 18–64 years) identified as transgender.37 In another large population-based survey in the Netherlands, 1.1% of those assigned male at birth (age 15–70 years) reported an incongruent gender identity (stronger identification with a gender other than the one assigned at birth), as did 0.8% of those assigned female at birth.38
Recent surveys of youth showed even higher numbers. In New Zealand, 1.2% of high school students surveyed identified as transgender.39 In a survey of San Francisco middle school students (grades 6–8), 1.3% identified as transgender.40 More study is needed, but these larger numbers indicate that many transgender people have not been counted in clinical studies, including those with nonbinary identities, those not seeking transition care, those receiving hormones outside of clinics specializing in transgender care or by self-administration, and others who identify as transgender when surveyed, but do not report gender dysphoria to clinicians.
Gender Development
Biological considerations
Animal research has established that sex differences in the phenotype of both body and brain as well as behaviors are the result of multiple, sex-biasing factors. These include hormonal, sex-chromosomal,41 genetic, and epigenetic contributions.42 The sensitivity of brain tissues to organizational effects of sex hormones appears to be particularly high at prenatal/perinatal stages of development and gradually declines toward young adulthood.43 The timing of hormonal secretions in the course of development, however, gives the impression of three discrete sensitive periods: (1) pre/perinatal; (2) pubertal44; and (3) for females, the first pregnancy.45
In humans, statistical sex differences in brain structure are well documented,46 and findings of sensitive periods for sexual differentiation of the brain appear to parallel those seen in other mammals.47,48 The evidence for brain/behavior effects of prenatal androgenization is particularly strong,49–51 much of which derives from studies of individuals with somatic intersex conditions and varying degrees of functional androgen exposure.51–53
Androgenization of the brain depends not only upon the level of androgen to which a fetus is exposed but also upon numerous other factors, including the presence of enzymes to convert androgens to the specific metabolites required by particular brain cells, their steroid receptors, and their postreceptor mechanisms that are involved in the full response to androgens. Receptor structure, which can influence sensitivity, is genetically determined, while the activity of genes for receptors and postreceptor mediators is subject to epigenetic modulation.54
As the period of genital differentiation largely precedes the sexual differentiation of the brain,55 it is conceivable that GD in individuals without somatic intersex conditions could reflect a brain-limited intersex condition (i.e., a lack of concordance between the sexually differentiated state of the brain and body). That hypothesis has been tested in a variety of ways, including searching for features of the brain in individuals with GD that more closely match their experienced gender than their birth-assigned gender.56 Investigations in this regard have included postmortem morphometric and stereological studies,57 as well as in vivo morphometric,58 functional magnetic resonance imaging,59 and diffusion tensor imaging studies of the brain,60–62 and examination of otoacoustic emissions.63
As reviewed elsewhere,53,56,64 while some positive findings in the predicted direction have been reported,56,64 inferences are currently limited. This is because few findings have been replicated and few studies have adequately controlled for potentially confounding variables such as age, sexual orientation, transition status (including history of gender-affirming hormonal treatment, if any), and hormonal status at the time of study (or of death in the case of postmortem studies).53
Much of what is known about the role of early hormonal exposure on the development of gender identity in humans derives from studies of gender outcomes in individuals with somatic intersex conditions. Early guidelines for initial gender assignment for such infants relied heavily on the surgical potential to achieve concordance between the gender assigned and the appearance and functional potential of the external genitalia, in particular, the capacity of penile-vaginal intercourse.9 Current guidelines, however, emphasize what is known about the long-term gender outcomes of individuals with intersex conditions on a syndrome by syndrome basis.52
Overall, these data suggest that regardless of genetic constitution, or gonadal or genital development at birth, individuals prenatally exposed to a full complement of masculinizing hormonal influences (i.e., androgen exposure and the cellular mechanisms for responding fully to androgens as described above) have an increased likelihood of GD when assigned female.51,52 Conversely, most reported 46,XY individuals with complete androgen insensitivity syndrome (and hence no functional androgenization of the brain) have developed a female gender identity, despite having a Y chromosome as well as normally developed and functioning testes.51,52 To date, however, no brain marker of sexual differentiation has been validated to guide the initial gender assignment of infants with intersex conditions.
Psychosocial factors influencing gender expression
In mammals, and particularly in humans, psychological and social factors have a major additional influence on behavioral outcome.65 In humans, these psychosocial processes include verbal labeling (e.g., “boy” and “girl”) and nonverbal gender-cuing (e.g., gender-specific clothing and haircuts) of children by parents and others in their social environment, as well as the shaping of children's gendered behavior by positive and negative reinforcement and later by explicit statements of gender-role expectations. Related processes in developing children include gender-selective observational learning/imitation, the formation of gender stereotypes and of related self-concepts, and self-socialization. The effects on gender development have been documented in a vast body of research in developmental psychology.65
The impact of such psychosocial factors, however, is not determinative. This is evidenced by individuals in whom gender identity is discordant with the initial gender assignment and gender of rearing, for example, transgender individuals and a higher than expected proportion of individuals with particular intersex conditions (i.e., 46,XY individuals with high degrees of somatic hypomasculinization and 46,XX individuals with high degrees of somatic hypermasculinization66,67).
Factors in gender-identity development
Systematic data on gender identity development are much more limited than those on gendered behavior. Yet, the data available, especially for those with intersex conditions, lead to the conclusion that, while early androgenization plays a role, a definitive biological predetermination of gender identity seems unlikely. Not a single biological factor, but multiple factors (i.e., biological, psychological, and social) appear to influence the development of gender identity.50
The need to transition gender is even less understood in individuals without, compared to those with, intersex conditions.68 Along with the dramatically increased referrals of gender-variant individuals to specialized clinics in Western Europe and North America over the last two decades,69,70 there has been a diversification of presentations beyond the original “transsexual” who sought (or was perceived by providers to seek) change to the “other” gender through treatment with gender-affirming hormones and genital surgeries. Currently, many transgender people seek chest, but not genital surgery, or only gender-affirming hormones, or only a social transition without any medical changes. Others may simply desire flexibility in gender expression without transition to “the other gender,” identifying, for example, as nonbinary or genderqueer.71,72
Prospective follow-up studies of children, who before puberty had met criteria for the DSM-IV diagnosis of GID, showed that the majority of those diagnosed with GID in early or early middle childhood “desisted,” meaning that they subsequently identified as their birth-assigned gender and did not meet criteria for GID. As adults, many identified as lesbian, gay, or bisexual.73–75 Some “desisters,” however, subsequently transitioned later in life.73
The data available do not allow a clear prediction before puberty of which child will persist and transition permanently, and which child will not.75 With the introduction of stricter criteria for the diagnostic category of Gender Dysphoria in DSM-5, the persistence rate likely will be higher,73 but this needs to be tested by future long-term follow-up studies. For example, the degree of gender nonconformity and whether a child believes they are, as opposed to wishes to be, “the other” gender have been proposed as predictors of persistence.76,77 Those in whom GD persists from childhood into adolescence are likely to experience an exacerbation of dysphoria with the emergence of (or with the anticipation of) undesired secondary sexual characteristics at puberty, in which case pubertal suspension should be considered.10
Regardless of their initial sexual orientation, during and after transitioning to express their experienced gender, some individuals retain their pretransition sexual attraction patterns, while others change.7 In some transgender women, the desire to transition gender is preceded by fantasizing themselves as women, sometimes with sexual arousal.78 This phenomenon has been controversially interpreted by some as fetishism.79 Importantly, neither a history of fetishistic arousal nor one's sexual orientation precludes one from meeting the criteria for the diagnosis of GD27 or eligibility for gender transition services.7,80
Mental Health Assessment and Treatment
This section addresses the assessment and treatment of adults with gender identity or expression concerns in the absence of an intersex condition. GD in individuals with intersex conditions is addressed in the Appendix. Treatment of GD in prepubescent children, where there is currently less consensus,81 is addressed elsewhere as is treatment of adolescents, including selection of candidates for pubertal suspension.81,82 The primary roles of the mental health professional in assessing and treating patients with GD are based on expert consensus,7,8,10,20 summarized in Table 2 and described more fully below in the broader context of gender variance.
Table 2.
Roles of the Psychiatrist
Assess and diagnose gender concerns according to current DSM criteria and see that they are addressed.
Assess and diagnose any coexisting psychopathology and see that it is addressed.
Assess eligibility for hormonal and/or surgical treatments, or refer to professionals capable of making such assessments.
Assess capacity to give informed consent for hormonal and surgical treatments.
Ensure that eligible individuals are aware of the full range of treatment options and their physical, psychological, and social implications, including risks, benefits, and impact on sexual functioning and reproductive potential.
Ensure adequate psychological and social preparation for transition treatments.
Refer patients for hormonal or surgical treatments, collaborating with providers as needed.
Ensure continuity of mental healthcare as indicated throughout transition and beyond.
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Expert consensus regarding the treatment of adults has been arrived at after many years of clinical experience. Attempts to engage individuals in psychotherapy to change their gender identity or expression are currently not considered fruitful by the mental health professionals with the most experience working in this area7,9,83 and legal bans of therapies aimed at changing sexual orientation have recently been extended to therapies aimed at changing gender identity or expression in a number of U.S. states and Canadian provinces.84,85 Currently, psychotherapeutic involvement with adults with GD is primarily used to assist in clarifying their desire for, and commitment to, changes in gender expression and/or somatic treatments to minimize discordance with their experienced gender, and to ensure that they are aware of and have considered alternatives.7
Gender questioning, gender-variant, and transgender adults present to mental health services for a variety of reasons. Some presentations may relate explicitly to gender. For example, patients may wish to explore their gender identity, consider transition options and concerns (e.g., coming out to family or coworkers), or request evaluation for hormonal or surgical treatments. The latter may include requests for referrals for such treatments, including requests for mental health referral letters as specified by the WPATH SOC7 or required by their providers of transition treatments and/or insurance carriers.7,11–13
According to WPATH SOC7, as an alternative to an evaluation by a mental health professional, primary care providers who are competent in the assessment of GD may evaluate patients for hormone therapy, particularly in the absence of significant coexisting mental health concerns and when working in the context of a multidisciplinary specialty team.7
Patients may also seek couples or family therapy before, during, or after transition to address the impact of the transition on interpersonal or family dynamics. Alternatively, many transgender patients seek or are referred to psychiatric services for reasons that are either unrelated to gender identity or expression (e.g., management of primary psychiatric illnesses), or only partially related (e.g., sequela of childhood trauma as a result of minority stress due to gender nonconformity).
A careful evaluation for a history and psychological sequela of gender-related stigma and abuse, from childhood on, is crucial given the high rates of violence and bullying experienced by gender-variant individuals, as well as the high rates of discrimination, unemployment, homelessness, sex work, and HIV infection.3,86 High rates of depressive, anxiety, and substance use disorders, as well as suicidal ideation and completed suicide have been linked to such gender minority stress.87–89 In addition to these mental health disparities, the transgender population also exhibits marked general health disparities.90 Few of these disparities are linked to sexually transmitted infections or hormonal or surgical transition treatments,7,10,90 but are instead linked to financial barriers to care as well as avoidance of healthcare due to experienced and/or anticipated stigma and discrimination in healthcare settings, and the widespread belief among transgender individuals that medical professionals are poorly trained to meet their needs,3 a belief that appears to be well-founded.15 Extensive guidance on overcoming these barriers to care, including creating a welcoming clinical environment, can be found elsewhere.91
Assessment of gender concerns
Treatment should be patient centered and tailored to the needs and individuality of each patient. Patients should be asked what names and pronouns they use and should be addressed by those names and pronouns regardless of their stage of transition. Those who transitioned many years ago and are seeking treatment for another problem typically need much less focus on gender history than those who are questioning their gender identity, just beginning gender transition, or exploring options for gender expression. When gender is not the primary concern, devoting the appropriate amount of attention to gender-related issues is important, balancing against an overemphasis on gender that can feel inadvertently stigmatizing to the patient or distract from adequate focus on the chief complaint.
While it is important to avoid the assumption that coexisting psychiatric symptoms are due to gender variance, the impact of past and present gender-related stigma should be considered in the biopsychosocial evaluation. This is particularly important in light of the stress-diathesis model of psychiatric illness and its exacerbations.8,92 Suicidality should always be assessed, as should protective factors such as social and family supports.93 Suicidal ideation3,94 and completed suicide90 are dramatically increased in this population and GD may be a risk factor for suicidality, independent of other psychiatric conditions.94,95 Up to 47% of transgender adults have considered or attempted suicide.93 Assessment of suicide risk is especially important during periods of heightened vulnerability, such as when transgender identity is disclosed to family and more broadly.9,83
The gender assessment should include the age and circumstances when the patient first became aware of a sense of difference from peers of the same sex assigned at birth as well as experiences of negative affect or self-perception related to that sense of difference.8,20 Any history of peripubertal and/or pubertal distress due to the anticipation and/or emergence of unwanted secondary sex characteristics should also be explored, as should past experiences of gender-related stigmatization, discrimination, harassment, and violence.8,20
The patient's history of coping mechanisms and support systems should also be examined.8,20 Gender expression (e.g., pronoun use, name changes, manner of dress, and bodily modifications) over time should be explored as well as what has and has not been helpful in improving the sense of well-being. It is important to clarify each patient's goals and plans for social and/or medical transition, degree of commitment, and expectations.7,96 For those who do not wish to transition, assessing current psychosocial challenges and formulating with the patient how to best address them (e.g., psychotherapy, group therapy, and social support) should not be neglected.
Recommendations regarding psychiatric assessment of individuals with GD have focused largely on assessment of eligibility for and decision-making capacity related to medical and surgical gender transition services.7,8,10 Eligibility for both gender-affirming hormone therapy and surgeries requires persistent gender dysphoria, a documented diagnosis of GD based on DSM-5 criteria, and the capacity to give informed consent.7 In addition, any significant medical or psychiatric concerns must be sufficiently controlled so that they do not interfere with the patient's ability to safely adhere to the treatment regimen. The current standard of care in major clinics, the WPATH SOC7, and insurance requirements for reimbursement of services follow a flexible progression of transition steps, which may begin with completely reversible steps (e.g., change of pronouns, name, and manner of dress), followed by partially reversible changes (e.g., gender-affirming hormones), and then irreversible gender-affirming surgeries.7,10–14,97 There is flexibility in this process given that some people do not pursue all of these interventions or may prefer to do so in a different sequence. For example, transgender men may wish to undergo mastectomy or male breast construction before initiating masculinizing hormones.7
Before gonadectomy, 12 months of continuous hormone therapy consistent with the patient's gender goals are recommended, unless hormones are clinically contraindicated for the individual. The aim of hormone therapy before gonadectomy is primarily to allow the individual to experience a period of gender-affirming hormones, before irreversible surgical intervention.7 Before masculinizing or feminizing genital reconstructive surgeries, the WPATH SOC7 also recommend 12 continuous months of living in a gender role that is congruent with the patient's gender identity.7
Diagnosis of gender dysphoria
The DSM-5 diagnostic criteria for GD in adolescents and adults are shown in Table 3. Diagnosing GD in adults by these criteria is usually straightforward, especially for those with overt manifestations in childhood, exacerbation of distress with pubertal changes, and persistence into adulthood in the absence of significant coexisting mental health concerns.8,9
Table 3.
Diagnostic Criteria for Gender Dysphoria in Adolescents and Adults
A marked incongruence between an individual's experienced/expressed gender and assigned sex as evidenced by two of the below, which have been present after the onset of puberty for at least 6 months:
A marked incongruence between one's experienced/expressed gender and primary and/or secondary sex characteristics (or the anticipated secondary sex characteristics in young adolescents).
A strong desire to be rid of one's primary and/or secondary sex characteristics because of a marked incongruence with one's experienced/expressed gender (or a desire to prevent the development of the anticipated secondary sex characteristics in young adolescents).
A strong desire for the primary and/or secondary sex characteristics of another gender.
A strong desire to be of a gender different from one's assigned gender.
A strong desire to be treated as a gender different from one's assigned gender.
A strong conviction that one has the typical feelings and reactions of a gender different from one's assigned gender.
The condition is associated with distress or impairment in social, occupational, or other important areas of functioning that are clinically significant.
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Adapted from DSM-5.27
Assessment of patients who are seeking transition services, but do not clearly meet criteria for GD, may require more time and exploratory therapy9 (e.g., a patient desiring hormonal or surgical treatment to transition to another gender, who does not clearly experience incongruence between their experienced gender and their gender assigned at birth). The same is true for those with the onset of gender dysphoria in the context of a psychiatric disturbance (e.g., psychosis, dissociative disorder, and autism spectrum disorder) or recent trauma9,98,99; those who are ambivalent about their gender identity or desired sex characteristics; and those who exhibit marked exacerbations and remissions of dysphoria over time.
The psychiatrist must assess whether some factor other than GD accounts for the expressed desire to transition. If not, coexisting mental illness is not a contraindication to supporting transition if it is sufficiently controlled to not interfere with the patient's capacity for decision-making or ability to safely adhere to the demands of the desired treatment.7,9,98
Differential diagnosis
Few conditions can be mistaken for GD. Simple nonconformity to gender roles can be differentiated from GD based on the degree of associated distress and whether or not the individual identifies as the sex assigned to them at birth. GD can be differentiated from body dysmorphic disorder (BDD), in which an individual may wish a body part to be removed or altered because it is viewed as deformed.27 In contrast, in GD alterations are sought for anatomical characteristics that are incongruent with one's gender identity. BDD and GD can, however, coexist and the presence of BDD is not an absolute contraindication for gender-confirming surgery.27 Transvestic disorder is characterized by significant distress or impairment due to sexual arousal in the context of cross-dressing fantasies, urges, or behavior. It may exist independently or co-occur with GD,27 and is not a contraindication to supporting transition in those who meet criteria for GD.7
Gender-themed delusions have been reported to occur in up to 20% of those with psychotic disorders.100 Such delusions can usually be easily differentiated from GD by their content (i.e., if they do not entail the belief that one's gender differs from that assigned at birth), as well as by their presence only during psychotic phases of illness, and the absence of other DSM criteria required for the diagnosis of GD.98 Importantly, GD and psychotic disorders may coexist and patients with both diagnoses can benefit from gender-affirmative treatment and appropriate hormonal and/or surgical gender interventions.98 Timely diagnosis of GD may be impeded when it is first overtly expressed in adolescence or early adulthood coincident with, or shortly following, the first psychotic episode.98
Mental health treatment
Statements in this section are based on the cited studies supplemented by the authors' cumulative clinical experience treating patients with GD. Psychotherapy can be useful for patients with GD; however, many successfully transition or decide against transition with little or no psychotherapy. Psychotherapy may be helpful at different times and for different reasons across the lifespan.7 Many transgender people seek mental health treatment on an intermittent basis, while contemplating gender transition, at key points in the transition process, or post-transition if symptoms recur or worsen.
Participation in transgender support groups, including peer-led groups, and other interactions with transgender individuals or the transgender community are often useful in clarifying the goals of those who experience ambivalence about transition. With patients who are otherwise eligible for transition treatments, but express ambivalence about transition, the therapist should maintain a stance of neutrality, creating a safe therapeutic space in which the patient can weigh all options and arrive at a decision in their own time. Many transgender adults need some combination of hormonal treatment and/or surgical procedures for relief of GD, but some experience relief with a change in gender expression without any medical treatment.7 Strengthening resilience factors identified in the transgender population93 should be a focus, particularly, in patients with suicidal ideation.
Although treatment with exogenous estrogen or testosterone carries a risk for medical side effects,10 both have been associated with improvement with respect to anxiety, mood, and mood stability, as well as overall satisfaction and quality of life for both transgender women and transgender men.101–104 Similarly, review of the available literature9 demonstrates the benefits of surgery in alleviating GD and the rarity of postsurgical regret. Emotional changes may occur with use of either androgen or estrogen supplementation, although these are usually subtle.9 An increase in libido usually occurs with androgen use with female to male transition.10 Although decreased libido due to antiandrogen and/or estrogen treatment in individuals transitioning male to female is common,10 some may experience a stronger interest in sex, perhaps due to the affirming aspects of attaining desired bodily changes.
Safer sex information and instruction in self-protective negotiation in sexual settings should be provided and tailored to the anatomy, needs, and experiences of transgender persons.9 Masculinizing hormones have been associated with a possible destabilization of psychotic and bipolar disorders, especially with supraphysiological blood levels of testosterone7 in both cisgender and transgender men.105–106 The likelihood of such episodes can, therefore, be minimized by careful dosing and monitoring.
Detailed information on specific gender-affirming surgical procedures can be found elsewhere.7,107 Psychiatrists should collaborate with other providers (e.g., endocrinologists, surgeons, psychotherapists, primary care providers, social workers, and other mental health professionals) to ensure that patients have the knowledge required to adequately evaluate the benefits, risks, and limitations of desired treatments and their alternatives. This is necessary not only for informed consent but also to ensure adequate preparation for surgery and postsurgical needs (e.g., convalescent period, period of sexual abstinence, and vaginal dilatation in the case of vaginoplasty).
Helping the patient anticipate and prepare for psychosocial impacts of treatment (e.g., impact on social relationships and employment) is also essential. Importantly, transition treatments target GD, not coexisting psychiatric diagnoses, and coexisting diagnoses are likely to require ongoing attention after transition, although symptom severity may be ameliorated.98,100,102
Referrals for hormones and surgery
Whether the initial evaluation for hormones is done by the hormone prescriber or by a mental health professional, criteria for starting hormones are the same: the presence of persistent GD, the ability to give informed consent, and relative mental health stability.7 Insurance carriers and surgeons require mental health evaluation before transition-related surgeries to assess and document eligibility, readiness, and medical necessity of the requested procedure.7,10–14
The specific requested content of referral letters varies among surgical providers and insurance plans. To avoid unnecessary delays in treatment, letter writers should be aware of such differences and ensure that their letters meet the requirements of all relevant parties. The content requested by most providers and insurance carriers is similar to that outlined in the WPATH SOC7. Genital and gonadal surgeries usually require documentation from two licensed mental health professionals, while chest surgeries generally require just one evaluation and referral.7,108 Although not requirements of WPATH SOC7, some insurers require one letter from a psychiatrist or other doctoral level mental health provider, or may specify a minimal duration of mental healthcare.13 Such requirements vary by health system, insurance carrier, and state, and raise challenges for those without access to reimbursement for mental healthcare.
Current Social Issues: Stigmatization and Access to Care
Transgender health advocates have worked to address societal discrimination against transgender people, including stigmatization of identity, discrimination in schools, workplaces, and healthcare, and to improve access to care. Increasingly, this advocacy has been embraced by major institutional and governmental agencies. One large online survey, the National Transgender Discrimination Survey88 found that rejection, discrimination, victimization, and violence against transgender people occur in a multitude of settings and negatively affect transgender people across the life span. Transgender youth are often harassed and assaulted in schools, which is associated with dropping out and subsequent impoverishment. Many transgender people are harassed at work or lose jobs due to their gender identity and expression. Discrimination extends to healthcare settings, where patients may be refused care or treated disrespectfully, or do not have access to care.88
U.S. public policy has contributed to the lack of access to care. A report by the National Center for Health Care Technology of the HHS Public Health Service issued in 1981, titled “Evaluation of Transsexual Surgery,” deemed these procedures “experimental,” and recommended that Medicare not cover transition-related care. This was formalized in a 1989 Health Care Financing Administration National Coverage Determination.5 Exclusion of transgender healthcare in private insurance as well as Medicaid and Medicare was near universal in the decades to come. A lack of funding for clinical care and research led to the closing of transgender care programs at academic institutions in the years following the 1981 report.
Many transgender health insurance exclusions have been removed recently. This trend started with increasing numbers of employers in the last 15 years adding transition care to health coverage. Starting in 2013, some states have ruled that transgender healthcare exclusions are discriminatory and have banned them from state-regulated health insurance plans. In 2014, the 1981 Medicare policy was reversed, removing categorical exclusions for transgender care.6 In 2015, the HHS moved to end categorical exclusions for transgender care from all insurance and care providers who accept federal funding or reimbursement;109 and since 2016, insurers in the Federal Employees Health Benefits Program must include transition-related coverage for transgender federal employees.110
During this same period, executive orders and other guidance from the Obama administration conferred increased protection against discrimination to transgender individuals in workplace and educational settings,111 the ban on open military service of transgender individuals was lifted,112 and changes at the HHS and the National Institutes of Health (NIH) facilitated research to better define and address the health needs of transgender individuals.111 Much work remains, however, to fully actualize these policy changes. In addition, progress has been slowed on the federal level by the change in presidential administrations and legal actions.113
WPATH SOC7 7 has attempted to improve access to care by including the informed consent model for hormone administration. In multidisciplinary clinics providing transgender care, primary care providers can assess for and diagnose longstanding GD that might benefit from treatment with hormones and administer hormones without referral from a mental health professional. However, patients with cooccurring mental health conditions should be referred to mental health providers when appropriate. WPATH has advocated for the depathologization of transgender identity, the medical necessity of transgender care, and improved access to legal gender change.7
The APA has also attempted to reduce stigma and improve access to care. As discussed previously, the DSM-IV diagnosis of GID, regarded as stigmatizing by many transgender health and advocacy groups, was replaced with GD in DSM-5.114 In addition, the APA approved position articles on discrimination and access to care. Its statement on discrimination against transgender and gender-variant individuals115 opposes all private and public discrimination against transgender individuals, and its statement on access to care for transgender and gender-variant individuals116 urged the removal of all categorical healthcare exclusions for transgender people and advocated for the expansion of access to care.
Increased access to care must be accompanied by culturally competent research in transgender health, recommended by the Institute of Medicine86 and outlined in the NIH's Strategic Plan to Advance Research on the Health and Well-being of Sexual and Gender Minorities.117 Expanded and improved education of healthcare providers is necessary, and the American Association of Medical Colleges has produced guidelines for curricular and climate change to improve transgender health.118 Principles of culturally competent care for transgender and nonbinary patients should be included in residency training as well, including psychiatric residency programs.
Conclusions
Transgender, nonbinary, and gender questioning people are sufficiently common that even psychiatrists whose practice does not focus on gender are likely to encounter patients who have transitioned gender, are planning or considering transition, or are questioning their gender identity. Gender concerns are only one of the reasons these individuals may seek psychiatric care and, regardless of their area of specialization, psychiatrists should be adept at conducting respectful, culturally sensitive, and affirming gender assessments without placing an undue emphasis on gender when it is not the patient's presenting concern. Mental health professionals must fully appreciate that the focus of treatment for GD is on the dysphoria, not the gender identity. At the same time, they must appreciate the role of minority stress in gender minority mental health disparities, screen for related manifestations, including anxiety disorders, depression, and suicidality, and consider resilience factors in treatment planning.
Psychiatrists should also be competent in the provision of routine psychiatric care that is gender affirming to gender variant patients with serious mental illnesses without assuming that the gender variance is a manifestation of the illness. They should not expect coexisting serious mental illness, especially in the context of strong genetic loading, to fully resolve with successful treatment of GD and should assist the patient in formulating realistic expectations.
If not included in their residency or fellowship training, or supervised clinical experience, psychiatrists should familiarize themselves with the standards of care for gender transition as described in the WPATH SOC7 and outlined in this article, as well as the roles and minimal competencies of mental health professionals working with adults with GD.7 In addition to the minimal competencies, WAPTH SOC7 recommends that health professionals take steps to sustain or augment their cultural competency to work with transgender and other gender minority patients by participating in continuing education and becoming knowledgeable about community, advocacy, and public policy issues that affect transgender individuals and their families.7
All providers should work within their sphere of competency and refer patients when necessary. Board-certified psychiatrists should be competent in the diagnosis of GD by the criteria of the most current DSM and in assuring that any coexisting psychiatric disorder is appropriately diagnosed and adequately controlled.118 In the absence of additional training, they should refer to other providers or seek supervision in fulfilling the other tasks of mental health professionals in addressing the gender concerns of transgender and other gender diverse patients. Providers from all disciplines should work within their professional organizations to ensure that training in gender-affirmative care is integrated throughout all levels of the training curriculum.119
Abbreviations Used
APA
American Psychiatric Association
BDD
Body Dysmorphic Disorder
DSM
Diagnostic and Statistical Manual of Mental Disorders
GD
Gender Dysphoria
GID
Gender Identity Disorder
GIDAANT
Gender Identity Disorder of Adolescence and Adulthood Nontranssexual Type
GIDC
Gender Identity Disorder of Childhood
HBIGDA
Harry Benjamin International Gender Dysphoria Association
HHS
U.S. Department of Health and Human Services
ICD
International Classification of Diseases
NIH
National Institutes of Health
SOC
Standards of Care
WPATH
World Professional Association for Transgender Health
Appendix
Gender Dysphoria in Patients with Intersex Conditions
As reviewed elsewhere,A1 Gender Dysphoria (GD) and patient-initiated gender transition occur with increased frequency in individuals with intersex conditions. Because Diagnostic and Statistical Manual of Mental Disorders-5 now allows gender-dysphoric individuals with somatic intersex conditions to receive the diagnosis of GD, psychiatrists need to be aware of assessment- and treatment-relevant characteristics of such individuals that differ from gender-dysphoric individuals without somatic intersexuality.A2
Intersex conditions are a subset of conditions relatively recently designated as “disorders of sex development”A3 or “differences of sex development” (DSD).A4 We use the term “intersex” in this document as our focus is on that subset of individuals with DSDs who were born with atypical external genitalia or lack of concordance among various sex characteristics such as sex chromosomes, gonads, or external genitalia so that questions often arise as to which gender should be assigned at birth. GD may develop from late preschool age through late adulthood with a range from 0% to ∼70% depending on the specific intersex syndrome, its severity (degree of androgen insensitivity, degree of 21-hydroxylase deficiency, degree of genital atypicality, etc.), the gender originally assigned, and the postnatal history of exposure to both endogenous and exogenous sex hormones.A5
Persons with the combination of GD and intersex condition encounter fewer barriers to legal gender reassignment, and the barriers to hormonal and surgical treatments are much lower.A1 This is because, depending on the particular condition, individuals with an intersex condition may have been gonadectomized (often due to concern about risk of malignancy) before puberty so that administration of exogenous hormones is required as part of routine care to induce puberty. In addition, infertility is quite common whether due to the condition itself or to gonadectomy, and genital surgery has often been done in infancy or childhood with the intent of affirming, both to the patient and the parents, the gender to which the individual was assigned. Furthermore, such early procedures may have been followed by additional surgical modifications in adolescence or young adulthood.
Decisions regarding hormonal and surgical procedures are complicated by the highly variable somatic presentations of the various intersex conditions. Thus, to be fully effective, the mental health provider needs to be informed about the medical and surgical history of the individual,A6,A7 the available data on long-term gender development (e.g., contentment vs. dysphoria in the assigned gender), and other psychological outcomes of patients on a syndrome by syndrome basis.A5,A8 Moreover, intersex conditions are frequently associated with stigma, even in medical settings, which may result in shame and maladaptive coping mechanisms on the part of the patients as well as their parents.A9–A12
Providers need to be aware of the many ways in which some individuals with intersex conditions report having been stigmatized by their treatment by clinicians and parents (e.g., failure of age-appropriate disclosure of their condition, attempts to modify their gender expression, and repeated genital examinationsA9,A13). Efforts are under way to develop decision-making tools and clinical checklists to ensure that parents and affected children are adequately assessed and informed as active participants in decision-making processes and that the intersex condition and its ramifications are disclosed to the affected individual in an age-appropriate manner.A14
Gender evaluation
The questionnaires and interview schedules developed for the assessment of gender development in transgender individuals who do not have an intersex conditionA15,A16 apply to those with intersex conditions as well, but need to be complemented by detailed medical, surgical, and related psychosocial histories, including the histories of disclosure to the patient of her/his medical condition, efforts made to reinforce the initial gender assignment, and responses by parents and providers to behaviors perceived as atypical with respect to the gender assignment. Mental health providers should also assess the patient's knowledge of their surgical history, their understanding of the implications with respect to fertility and gender-affirming hormonal and surgical procedures, and any history of shaming or other stigma due to their condition, or perceived gender atypicality with respect to their gender assigned at birth.
Decisions regarding gender transition
For individuals with intersex conditions, GD usually raises the question of transition to a different gender, and all issues of relevance to transgender persons without these conditions should also be considered here. Yet, the situation is often more complex than in GD in the absence of an intersex condition. Factors contributing to the desire to transition may include the awareness of the discrepancy between assigned gender and genetic factors such as the karyotype, anatomic factors such as the type of gonads, and secondary sex characteristics like breast development in men or hirsutism and masculine habitus in women. Related psychosocial influences may derive from being misidentified as the “other” gender or from frank stigmatization due to gender-atypical physical features.
Different cultures and even subcultures within a given country may differ in the roles (including rights) associated with one's gender, and in the salience and weight of criteria used in decision-making on gender reassignment.A17,A18 When discussing gender options, clinicians need to consider the legal regulations of the country in which they work as well as the religious and other ideologies that can influence the gender perspectives of patients (and of caregivers for minors). These considerations are also very important when doing clinical work with visitors or immigrants from foreign countries. Thus, the viewpoints of patients (and caregivers) within their cultural contexts should be explored in detail and taken into consideration when these individuals are provided with psychoeducation about gender and other issues related to their intersex conditions.A19
As with other transgender patients, when working with patients with an intersex condition and GD, clinicians should engage the patient in a detailed discussion of their expectations from the gender transition: the social effects of public gender change as well as the medical and social effects of the attendant change in hormone treatment and, if desired, of genital or chest surgery. Some of their expectations may be unrealistic, and after detailed discussion, some patients may modify the hormonal and/or surgical treatments they desire or decide against medical treatments or legal gender change, and pursue other ways of finding authenticity in their gender expression. Patients may be happy with their gender-atypical bodies and/or adapt a nonbinary gender identity such as “intersex.” Mental health providers should not assume that patients would benefit from conforming to fit within a gender binary, physically or with respect to gender identity.
Empathic listening is especially important in working with intersex individuals, perhaps particularly with those who have inadvertently discovered their intersex status in adolescence or adulthood, and may have been stigmatized for gender nonconformity or homosexuality, or subjected to irreversible hormonal or surgical treatments consistent with their assigned rather than their experienced gender. Upon discovery of their biological status, such patients may feel betrayed by their parents and physicians, feeling they colluded to keep them in ignorance of their medical condition, damaged their bodies, or punished or stigmatized them for their gendered behaviors. Such patients need empathic validation of their feelings. Assurance that parents and providers had their best intentions at heart, while usually true, is likely to be experienced as an empathic failure and negatively impact the formation of a therapeutic alliance.
As is often seen in many individuals with uncommon medical conditions, many people with intersex conditions experience varying degrees of isolation and loneliness.A1 Therefore, linking them to existing intersex support groups by internet or face-to-face meetings can be very beneficial. Despite the emotional relief that support groups can provide, such contacts may sometimes cause additional concerns. For instance, the composition of the group (e.g., the syndromes represented within the group, the personalities of some group members, or the goals of the group) may not meet the individual's expectations, and the information provided may not always be accurate. Thus, some monitoring of the patient's experience with the chosen group is recommended.
Hormonal and surgical treatments
As reviewed elsewhere,A1 many individuals with both an intersex condition and GD will be agonadal in later adolescence or adulthood, either because they were born that way (e.g., in syndromes involving gonadal dysgenesis) or due to surgery, for instance, for the prevention of gonadal malignancy. In those with intact gonads (especially 46,XX congenital adrenal hyperplasia raised female), loss of fertility may be another issue of concern. Persons who are agonadal are usually on hormone replacement therapy by the time of late adolescence. Cessation of that treatment, change to treatment with hormones congruent with their gender identity, patient education for informed consent, and the monitoring of treatment effects are tasks of the endocrinologist.
Also, the technical aspects of genital surgery are more complex than in patients receiving gender-confirming genital surgeries, who do not have intersex conditions. Both the external genitalia and the internal reproductive tract in intersex conditions typically differ from what most surgeons are familiar with in transgender patients without these conditions. In addition, many patients with intersex conditions have already undergone one or more genital surgeries by late adolescence. The resulting postsurgical anatomy constitutes an additional challenge for the surgeon performing gender-confirming surgery, and a good sex-functional outcome may be more difficult to achieve.
Mental health providers should also be aware that not all individuals who identify their gender or gender identity as intersex have a somatic intersex condition, and should ensure that those who do have an intersex condition are receiving adequate medical care, including hormones (to prevent osteoporosis) and cancer screenings, as appropriate to their particular condition.A3 Without challenging a patient's identity label, this distinction can usually be made by inquiring about the name of the patient's condition, when and how they learned of it, and any history of related surgeries, hormonal replacement, or ongoing follow-up evaluations. If there is any doubt, appropriate referrals should be made to ensure that the patient is receiving adequate follow-up and treatment.
Appendix References
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Author Disclosure Statement
No author has any conflict of interest to report.
Cite this article as: Byne W, Karasic DH, Coleman E, Eyler AE, Kidd JD, Meyer-Bahlburg HFL, Pleak RR, Pula J (2018) Gender dysphoria in adults: an overview and primer for psychiatrists, Transgender Health 3:1, 57–A3, DOI: 10.1089/trgh.2017.0053.
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Abstract
Introduction
Diagnostic and Statistical Manual of Mental Disorders and Transgender-Related Nosology
Epidemiology
Gender Development
Mental Health Assessment and Treatment
Current Social Issues: Stigmatization and Access to Care
Conclusions
Abbreviations Used
Appendix
Author Disclosure Statement
References
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