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Chem GRE > P Chem > Flashcards

P Chem Flashcards

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1
Q

Bohr Atom Energy

A

En = 13.6 eV / n^2

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2
Q

Nodes

A

Total: n - 1
Radial: n - l - 1
Angular: l

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3
Q

First Law of Thermodynamics

A

dU = q + w

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4
Q

Cp/Cv relationship

A

Cp - Cv = nR

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5
Q

PV work with Pext

A

w = -P(ext) (Vf - Vi)

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6
Q

Solving 1st Law for Q

A

q = dU - w = dU + P(ext)dV

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7
Q

Irreversible process work

A

w = - nRT ln(V2/V1)

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8
Q

Internal Energy with C

A

dU = qv = Cv(Tf - Ti)

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9
Q

Enthalpy/Interal Energy relationship

A

H = U + PV = U + nRT

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10
Q

Enthalpy with C

A

dH = qp = Cp(Tf-Ti)

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11
Q

Carnot efficiency

A

e = 1 - Tcold/Thot

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12
Q

Entropy, general

A

dS = nR ln(Vf/Vi) = -nR ln(Pf/Pi)

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13
Q

Entropy at constant V

A

dS = n Cv,m ln(Tf/Ti)

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14
Q

Entropy at constant P

A

dS = n Cp,m ln(Tf/Ti)

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15
Q

Entropy at phase change

A

dS = dHvap / dTvap (or fus)

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16
Q

Total entropy

A

dS(total) = dS + dS(surroundings)

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17
Q

Second Law of Thermodynamics

A

The entropy of an isolated system never decreases

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18
Q

Third Law of Thermodynamics

A

The entropy of a pure, perfectly crystalline substance is zero at zero kelvin

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19
Q

Absolute entropy

A

S = k ln (W)

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20
Q

DOF nonlinear gas molecule

A

3 Translational
3 Rotational
3n - 6 Vibrational

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21
Q

DOF linear gas molecule

A

3 Translational
2 Rotational
3n - 5 Vibrational

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22
Q

The entropy of all substances is a…

A

monotonically increasing function of temperature

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23
Q

Helmholtz Free Energy

A

A = U - TS

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24
Q

Gibbs Free Energy

A 
G = H - TS
G = U + PV - TS
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25
Q

dU

A

dU = TdS - PdV

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26
Q

dH

A

dH = TdS + VdP

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27
Q

dA

A

dA = -SdT - PdV

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28
Q

dG

A

dG = -SdT + VdP

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29
Q

Isobaric volumetric thermal expansion coefficient

A

a or b = (1/V) (dV/dT)_P

30
Q

Isothermal compressibility

A

k = -(1/V)(dV/dP)_T

31
Q

Gibbs-Helmholtz Equation

A

[d(G/T)/dT]_P = -H/T^2

32
Q

dS(mixing)

A

dS(mixing) = -nR sum(xi ln(xi))

33
Q

dG(R)

A

dG(R) = dG(R0) + RT ln Q

34
Q

G/K relationship

A

dG = -RT ln K

35
Q

K/T dependence

A

ln K@Tf = ln K@T0 - (dH/R)(1/Tf - 1/T0)

36
Q

Error in IDG

A

z = Vm/Vm(ideal) = PVm/RT

37
Q

Boyle temperature

A

Tb = a/Rb

38
Q

An increase in P always leads to…

A

a boiling point elevation

39
Q

Freezing point is elevated with increased P if…

A

V liq > V solid

40
Q

Freezing point is depressed with increased P if…

A

V liq < V solid

41
Q

dH(sublimation)

A

dH(sub) = dH(fus) + dH(vap)

42
Q

Gibbs’s Phase Rule for pure system

A

DOF = 3 - p

43
Q

Clapeyron Equation

A

dP/dT = dSm/dVm

Slope of coexistence curve!

44
Q

Trouton’s Rule

A

dSm(vap) ~ 90 J/mol*K for liquids

45
Q

Clausius-Clapeyron Equation

A

ln(Pf/Pi) = -(dHm(vap)/R) (1/Tf - 1/Ti)

46
Q

Raoult’s Law

A

Pi = xi Pi*

47
Q

DOF for system with C components

A

DOF = C - p + 2

48
Q

Gibbs-Duhem equations

A

n1dmu1 + n2dmu2 = 0
x1dmu1 + x2dmu2 = 0
x1dV1 + x2dV2 = 0

49
Q

Boiling Point Elevation

A

dT(boiling) = Kb*molality(solute)

50
Q

Freezing Point Depression

A

dT(freezing) = - Kf*molality(solute)

51
Q

van’t Hoff Equation

A

pi = n(solute)RT/V

52
Q

Ideal Solution characterized by…

A

dGmix < 0
dSmix > 0
dV mix = 0
dH mix = 0

53
Q

Henry’s Law for solute

A

Pi = xi kHi as xi –> 0

54
Q

Positive Deviation from Raoult’s Law

A

A-B interactions are least attractive
Minimum boiling azeotrope formed
kH > Pi*

55
Q

Negative Deviation from Raoult’s Law

A

A-B interactions are most attractive
Maximum boiling azeotrope formed
kH < Pi*

56
Q

Standard Solvent State

A

as xi –> 1,
ai = Pi/Pi*
gi = ai/xi

57
Q

Standard Solute State

A

as xi –> 0,
ai = Pi/kHi
gi = ai/xi

58
Q

G/E relationship

A

dG = -nfE

59
Q

E/K relationship

A

E = (RT/nF) ln K

60
Q

pH/pKa relationship

A

pH = pKa + log([A-]/[HA])

61
Q

Vibrational states…

A

are only significantly populated at high T

62
Q

Rotational states…

A

are populated at room T

63
Q

rate k/Ea relationship

A

ln(k) = -Ea/RT

64
Q

3 amino acids that have an isoelectric point not the average of their two lowest pKa’s

A

Arg, His, Lys

+ charged side chains

65
Q

U(translation)

A

UT = (3/2)nRT

66
Q

U(rotation)

A 
UR = nRT (linear polyatomic)
UR = (3/2)nRT (nonlinear polyatomic)
67
Q

U(vibration)

A

UV = nRT in high T limit

68
Q

U(electronic)

A

UE = 0

69
Q

Dulong & Petit Law

A

Limiting value of heat capacity of a solid is 3R at high T

70
Q

Debye modification to Einstein solids

A

Low T heat capacity is proportional to T^3

Chem GRE (5 decks)

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