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Chemistry 3321 > Exam 2 > Flashcards

Exam 2 Flashcards

(108 cards)

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1
Q

What are the natural variables of entropy?

A

V and U, since its coefficients in dS = PdV + (1/T)dU are simple thermodynamic quantities

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2
Q

Sketch out a generalized phase diagram.

A

sketch https://chem.libretexts.org/Textbook_Maps/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/Physical_Properties_of_Matter/States_of_Matter/Phase_Transitions/Phase_Diagrams

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3
Q

What is the triple point?

A

point on a phase diagram at which the three states of matter: gas, liquid, and solid coexist

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4
Q

What is the critical point?

A

point on a phase diagram at which the substance is indistinguishable between liquid and gaseous states

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5
Q

Sketch out the phase diagram for water and CO2.

A

sketch https://chem.libretexts.org/Textbook_Maps/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/Physical_Properties_of_Matter/States_of_Matter/Phase_Transitions/Phase_Diagrams

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6
Q

State Raoult’s Law.

A

the vapor pressure of a solvent above a solution is equal to the vapor pressure of the pure solvent at the same temperature SCALED by the mole fraction of the solvent present

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7
Q

Write out the generalized, undifferentiated form of the Helmholtz free energy.

A

A = U - TS

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8
Q

The sign of the Helmholtz free energy change denotes

A

the direction of a spontaneous process in a system at constant volume and temperature (i.e. if da <= 0)

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9
Q

Sketch out a diagram of Helmholtz free energy versus time.

A

sketch Dineli’s Exam 4 Notes, page 21

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10
Q

Write out the differentiated form of the Helmholtz free energy, and show the steps to get there.

A

ΔA = ΔU - TΔS

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11
Q

Write out the generalized, undifferentiated form of the Gibbs free energy.

A

G = H - TS

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12
Q

The sign of the Gibbs free energy change denotes

A

the direction of a spontaneous process in a system at a constant pressure and temperature (i.e. if dG <= 0)

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13
Q

Sketch out a diagram of the Gibbs free energy versus time.

A

sketch Dineli’s Exam 4 Notes, page 21

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14
Q

Derive the Maxwell relation for A.

A

derive Dineli’s Exam 4 Notes, page 22

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15
Q

Write out the equation for U.

A

U = q + w

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16
Q

What are the natural variables of U?

A

S and V

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17
Q

What is the differential expression for U?

A

dU = TdS - PdV

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18
Q

What is the Maxwell relation for U?

A

(∂T/∂V)S = -(∂P/∂S)V

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19
Q

Write out the equation for H.

A

H = U + PV

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20
Q

What are the natural variables of H?

A

S and P

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21
Q

What is the differential expression for H?

A

dH = TdS + VdP

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22
Q

What is the Maxwell relation for H?

A

(∂T/∂P)S = (∂V/∂S)T

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23
Q

Write out the equation for A.

A

A = U - TS

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24
Q

What are the natural variables of A?

A

V and T

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25
What is the differential expression for A?
dA = -PdV - SdT
26
What is the Maxwell relation for A?
(∂P/∂T)V = (∂S/∂V)T
27
Write out the equation for G.
G = H - TS
28
What are the natural variables of G?
P and T
29
What is the differential expression for G?
dG = VdP - SdT
30
What is the Maxwell relation for G?
(∂V/∂T)P = -(∂S/∂P)T
31
How do we calculate ΔG if we know the volume and the initial and final pressures?
ΔG = V*(Pf - Pi)
32
How do we calculate ΔG if we know the entropy and the initial and final temperatures?
ΔG = -S*(Tf - Ti)
33
What is the relationship between ∂G, ∂P, and V?
(∂G/∂P)T = V
34
What is the relationship between ∂G, ∂T, and S?
(∂G/∂T)P = -S
35
Write out the equation for the pressure dependence of G at constant T. Identify each component.
ΔGrxn = ΔG° + RT*lnQ — Dineli's Exam 4 Notes, page 25
36
Write out the expression for Q.
*write out* Dineli's Exam 4 Notes, page 25
37
Write out the formula for the temperature dependence of G at constant P. This expression leads us to what equation?
(G/T) = (H/T) - S, leads us to the Gibbs-Helmholtz equation
38
Write out the Gibbs-Helmholtz equation.
*write out* Dineli's Exam 4 Notes, page 25
39
Write out the secondary version of the Gibbs-Helmholtz equation.
*write out* Dineli's Exam 4 Notes, page 25
40
Which equation do we use when comparing the Gibbs energy of a reaction at two temperatures?
Gibbs-Helmholtz equation, secondary version
41
Write out the generalized ICE table for A + B ---> Y + Z.
*write out* Dineli's Exam 4 Notes, page 26
42
Write out the equation for chemical potential at constant temperature and pressure.
*write out* Dineli's Exam 4 Notes, page 26
43
When a reaction system is in equilibrium, ΔG =
0
44
At equilibrium, what is true about Q and Kp?
Q = Kp
45
Write out the equation for ΔG° given Kp.
ΔG° = -RT*ln(Kp)
46
Write out the expression for Kp.
*write out* Dineli's Exam 4 Notes, page 27
47
How can you calculate ΔGrxn without calculating ΔG°?
ΔGrxn = RT*ln(Q/Kp)
48
If Q < Kp, what is true about ΔG and the direction of the reaction?
ΔG < 0 and the reaction will shift to the right
49
If Q > Kp, what is true about ΔG and the direction of the reaction?
ΔG > 0 and the reaction will shift to the left
50
The equilibrium constant Kp is a function of
T and T only
51
What is Le Chatelier's principle?
if a chemical reaction at equilibrium is subjected to a change in conditions that displaces it from equilibrium, then the reaction adjusts toward a new equilibrium state
52
Draw a graph of reaction extent versus pressure.
*draw* Dineli's Exam 4 Notes, page 29
53
What is Kc?
equilibrium constant with concentration terms
54
Write out the expression for Kc.
*write out* Dineli's Exam 4 Notes, page 30
55
Write out the relationship between Kp and Kc. What assumptions do we make?
*write out* Dineli's Exam 4 Notes, page 30; P° = 1 bar and c° = 1 mol/L
56
Write out the equation relating Kp and two different temperatures. What is the name of this equation?
*write out* Dineli's Exam 4 Notes, page 31; Van't Hoff equation
57
Write out the equation for the chemical potential of substance i.
*write out* Dineli's Exam 4 Notes, page 32
58
What is the physical interpretation of the partial molar Gibbs quantity?
a measure of how G changes when ni is changed while keeping T, P and other mole numbers fixed
59
Write out the equation relating the chemical potential of a substance i and the chemical potential of its pure form. Identify each component.
*write out* Dineli's Exam 4 Notes, page 32
60
Write out the equations for G, S, and Vsoln for a liquid-liquid mixture.
*write out* Dineli's Exam 4 Notes, page 33
61
Write out the Gibbs-Duhem equation.
*write out* Dineli's Exam 4 Notes, page 33
62
Write out the Gibbs-Duhem equation for volume.
*write out* Dineli's Exam 4 Notes, page 33
63
At equilibrium, what is the relationship between the chemical potential of the solution and the chemical potential of the vapor?
µj(sol) = µj(vap)
64
What is the formula to calculate µj(vap)? Identify each component.
*write out* Dineli's Exam 4 Notes, page 34
65
What is the formula to calculate µ*j(vap)? Identify each component.
*write out* Dineli's Exam 4 Notes, page 34
66
What is the formula to calculate µj(sol)? Identify each component.
*write out* Dineli's Exam 4 Notes, page 35 + 36
67
Write out the equation for the chemical potential of an ideal solution in the context of Raoult's law, using activity.
*write out* Dineli's Exam 4 Notes, page 36
68
Write out the equation for the chemical potential of a non-ideal solution in the context of Raoult's law, using activity.
*write out* Dineli's Exam 4 Notes, page 36
69
What is Dalton's law?
total pressure of a system is the sum of the partial pressures exerted by each gas in the system
70
What is Henry's Law?
the amount of dissolved gas is proportional to its partial pressure in the gas phase
71
Write out the formula for activity.
*write out* Dineli's Exam 4 Notes, page 36
72
Write out Henry's Law for an ideal solute.
*write out* Dineli's Exam 4 Notes, page 36
73
Write out Henry's Law for a non-ideal solute.
*write out* Dineli's Exam 4 Notes, page 36
74
What is the generalized equation for equilibrium systems consisting of gases, solids, liquids, and/or solutions? Identify each component.
*write out* Dineli's Exam 4 Notes, page 37
75
What is the standard reference state for a gas and the corresponding expression for activity?
chemical potential of an ideal gas at 1 bar; aj = Pj/P°
76
What is the standard reference state for a solvent and the corresponding expression for activity?
Raoult's Law reference/state — chemical potential of pure component j; aj = Pj/P* and aj = γ*xj
77
What is the standard reference state for a solute?
Henry's Law reference/state — chemical potential of an ideal solution at unit molality or unit molarity
78
What are the three activity coefficient scenarios for the standard/reference state of a solute?
mole fraction scale; molality scale; molarity scale
79
Write out the activity expressions for the mole fraction scale.
*write out* Dineli's Exam 4 Notes, page 37
80
Write out the activity expressions for the molality scale.
*write out* Dineli's Exam 4 Notes, page 37
81
Write out the activity expressions for the molarity scale.
*write out* Dineli's Exam 4 Notes, page 37
82
Write out the expression for the extended Debye-Huckel equation. Identify each component.
*write out* Dineli's Exam 4 Notes, page 38
83
Write out the expression for ionic strength. Identify each component.
*write out* Dineli's Exam 4 Notes, page 38
84
What is the relationship between ΔS-bar-trans, ΔH-bar-trans, and T?
*write out* Dineli's Exam 4 Notes, page 38
85
Write out the two variants of the Clapeyron equation.
*write out* Dineli's Exam 4 Notes, page 38
86
What is the Clapeyron equation?
relates the slope of the two-phase boundary line in a phase diagram
87
Why can't we use the Clapeyron equation for liquid-to-gas or solid-to-gas transitions?
because the molar volume of a gas varies strongly with pressure
88
The Clapeyron equation is restricted to which transitions?
solid to liquid
89
Write out the two variants of the Clausius-Clapeyron equation.
*write out* Dineli's Exam 4 Notes, page 39
90
What are the three colligative properties discussed in this unit?
lowering of vapor pressure; freezing point depression; boiling point elevation
91
What is the simple formula for freezing point depression?
ΔTfus = Kf * m
92
In addition to P and T, what else does G depend on?
the number of moles of each species in the system
93
(∂G/∂P)T =
V
94
How do we convert the activities of two ionic species into their concentrations?
(αx+)*(αy-) = (cx+)*(cy-)*(γ+/-)^2 [combined lecture notes, page 9]
95
What is the phase rule?
degrees of freedom = 3 - (# phases in coexistence)
96
The solid-gas coexistence line gives vapor pressure as a function of
temperature
97
The solid-liquid coexistence line gives melting point as a function of
pressure
98
(∂G/∂T)P =
-S
99
The Clausius-Clapeyron equation is used for which transitions?
liquid-gas, solid-gas
100
Write out the derivation for the Clausius-Clapeyron equation.
*write out* [combined lecture notes, page 12]
101
Draw a graphical representation of the Clausius-Clapeyron equation. What is the slope of the line?
*draw* [combined lecture notes, page 12]; slope = -ΔHvap/R
102
What is the physical interpretation of partial molar volumes?
if you mix two substances, the total volume of the combined mixture might change because of intermolecular forces
103
Transfer dn1 moles of species 1 from solution to vapor. How does the free energy of the system change?
*write out* [combined lecture notes, page 14]
104
What is the physical interpretation of Raoult's Law?
surface composition is bulk composition
105
What is the complex formula for freezing point depression?
*write out* [combined lecture notes, page 16]
106
What is the complex formula for boiling point elevation?
*write out* [combined lecture notes, page 16]
107
What is the simple formula for boiling point elevation?
ΔTvap = Kb * m
108
What is the simple formula for osmotic pressure?
pi = R * T * c

Chemistry 3321 (3 decks)

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