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CHEMISTRY 123
Problem Set #1
Phase Equilibria
120. Below is the phase diagram for phenol, which has two solid phases, SI and SII, both more dense
than the liquid. The transition SI SII is exothermic.
Page 2 of 6
Identify the phase(s) present in each of the numbered regions on the following graphs.
1216. Isotherm of phenol at 50 C
Page 3 of 6
21. A substance has the following properties: boiling point = 75 C and melting point = 15 C. Sketch a
heating curve for the substance from 50 C to 100 C in the diagram shown below. Clearly label the
phases present at each individual step (five steps).
T [K]
373
273
223
Time [min]
2230. For H2O, the normal boiling point is 100 C; the normal melting point is 0 C; the triple point is
at 0.0098 C and 0.006 atm; the critical point is at 374 C and 220 atm. Only three phases are present at
the temperatures and pressures shown on the graph.
220
P(atm)
1.0
0.006
0.0
0.0098
374
100
T(C)
Page 4 of 6
22. Draw the phase diagram for H2O using the graph above.
23. Label the regions S (solid), L (liquid), and V (vapor).
24. Circle and label the triple point (T), the critical point (C), the normal boiling point (bp), and the
normal melting point (mp).
25. At 70 C, a rigid container is first evacuated, then half filled with water, sealed, and allowed to reach
equilibrium. Which phases are present in the end?
26. One of the unique properties of water is the relative density of the solid and liquid phases. Which
phase of H2O is more dense?
27. On the phase diagram, identify the curve that indicates the relative densities of the liquid and solid
phases, and label it with a D.
28. Is the slope of line D positive or negative? Explain in terms of the effect of pressure at constant
temperature.
29. Benzene freezes at +5.5 C. Although you can easily skate on a frozen lake of water at 5 C, you
would not be able to skate very well on frozen benzene at 0 C (i.e., also about 5 C below its
melting point). Explain why not by discussing the fact that the phase diagram for benzene is
normal. (Ignore toxicity.)
30. If youre skiing at the top of Whistler and youre cooking spaghetti in boiling water, why does it take
a bit longer than usual (i.e., compared to at home, at sea level) to cook? (Consider only the time after
which the spaghetti is added to the boiling water, not the time needed to heat the water to a boil.)
3134. A phase diagram for an unknown substance is shown below. This substance has a vapour and
liquid phase, and three solid phases (SI, SII, and SIII). At point A on the diagram, SIII, SII, and the liquid
phase are in equilibrium. SII is denser than SIII.
P
[atm]
T [K]
Page 5 of 6
31. Label the states present in each of the five regions of the phase diagram.
32. Label all triple points with TP and the critical point with CP.
33. Which phase present at point B has the higher density?
34. Sketch (not to scale) on the axis below the effect of decreasing pressure on the volume of the
substance along the dashed line on the phase diagram on the previous page.
P [atm]
35. Which of the following compounds is expected to have the highest vapor pressure?
(1) CH3CH2CH3
(2) CH3OCH3
(3) CH3CH2OH
(4) CH3CH2CH2CH3
(5) CH3CH2CH2Cl
36. The vapor pressure of a liquid increases with an increase in temperature. Which of the following
statements best explains this increase?
(1) The average kinetic energy of molecules is greater; thus more molecules can enter the gaseous
state.
(2) The average kinetic energy of molecules is less.
(3) The faster-moving molecules in the liquid exert a greater pressure.
(4) All the molecules have greater kinetic energies.
(5) The intermolecular forces between the molecules decrease at higher temperatures.
Page 6 of 6
37. Which compound should have the highest vapor pressure at room temperature?
(1) C4H10
(2) C5H12
(3) C6H14
(4) C7H16
(5) C8H18
38. Which of the following indicates the existence of strong intermolecular forces of attraction in a
liquid?
(1) a very low boiling point
(2) a very low vapor pressure
(3) a very low critical temperature
(4) a very low viscosity
(5) a very low heat of vaporization
39. Which of the following compounds would be expected to have the highest vapor pressure?
(1) CH3CH2CH2F
(2) CH3CH2CH2OH
(3) CH3CHCH3OH
(4) CH3CH2COOH
(5) CH3CH2CH2NH2
40. Which of the following has the lowest vapor pressure?
(1) H2O
(2) H2S
(3) H2Se
41. Which of the following accounts for the relatively high vapor pressure of diethyl ether liquid,
(CH3CH2)2O, at 25 C?
(1) density of the liquid
(2) strength of the intermolecular forces
(3) strength of the intramolecular forces
42. Of the following substances, which is expected to have the lowest normal boiling point?
(1) CH3OH
(2) CH3Cl
(3) CH4
(4) C2H6
(5) C3H8
Page 1 of 8
CHEMISTRY 123
1. 4
2. 1
3. 2
4. 2,3,4
5. 1,2,3
6. 4
7. 1
8. 4
9. 3
10. 2
11. 1,3
12. 1
13. 1,2
14. 2
15. 3
16. 4
17. 3
18. 2,3
19. 2
20. 1,2
Phase Equilibria
35. 1
36. 1
37. 1
38. 2
39. 1
40. 1
41. 2
42. 3
Detailed Solutions
17.
P
(atm.)
2000
C
61
B
1
D
0.003
40
64
420
T (C)
Page 2 of 8
The two solid phases, SI and SII, are denser than the liquid phase. Also, the liquid phase is denser
than the vapor phase. So the lowest density phase, D, must be vapor; C must be liquid; and B and A
must be SI and SII (but which is which is not yet determined).
The transition SI SII is exothermic:
SI SII + heat
When both solid forms are in equilibrium (along the A:B equilibrium line) and the heat in the system
is reduced by decreasing the temperature, the equilibrium will shift towards the SII side to generate
heat and relieve the stress on the equilibrium. Thus, SII is A, the lower temperature solid phase, and
SI is B, the higher temperature solid phase.
Solid SII
P
(atm.)
2000
liquid
C
61
Solid SI
1
D
0.003
vapour
40
64
420
T (C)
Note that 2000 atm and 64 C is a triple point where liquid, SI, and SII are all in equilibrium.
Note that 3 103 atm and 40 C is a triple point where vapour, liquid and SI are all in equilibrium.
8. A liquid boils when its vapour pressure equals the external pressure. The normal boiling point is the
temperature where the liquid phase boils when the external pressure is 1 atm. Therefore, the vapor
pressure of the liquid is also 1 atm at the normal boiling point. The horizontal line at 1 atm on the
phase diagram intersects the liquid-vapor equilibrium line (the vapor-pressure curve for the liquid) at
T = 200300 C. Thus, the normal boiling point is in the range of 200300 C (note: the b.p. is only
estimated because the temperature scale on the phase diagram is non-linear, which makes it difficult
to accurately read).
9. The critical point is the point (Pc, Tc) on the phase diagram where the liquid-vapor equilibrium curve
ends. This is at P = 61 atm and T = 420 C for this substance.
Page 3 of 8
10. SI is region B, and liquid is region C. Starting on the SI:liquid equilibrium line, increasing the
temperature (i.e. adding heat) causes a shift to the liquid. Therefore, SI liquid is endothermic:
SI + heat liquid
11. Vapor and SI would be in equilibrium. Starting at (P = 1 atm, T = 35 C), the phenol will be in the SI
form. If the tube could be pumped out very quickly and sealed, the pressure above the solid would
initially be very low and the system would not be at equilibrium. At a temperature of 35 C,
equilibrium would be attained by the solid subliming until the pressure above the solid was the
vapor-pressure of solid (SI) phenol at 35 C. On the phase diagram, the system would end up on the
SI : vapor equilibrium (SI vapor-pressure) line at a temperature of 35 C.
1216. An isotherm displays the path of an isothermal process (a vertical line on a PT phase diagram).
In this case, V vs. P is plotted as the pressure on the system is increased at 50 C. The path is
upward along the line T = 50 C on the diagram.
12. The initial conditions are P < 0.04 atm and T = 50 C. Under these conditions, the phenol is all in
the vapor phase. Considering the vapor to be an ideal gas with T, n, and R constant, the volume
is proportional to 1/P; hence the isotherm is hyperbolic in the vapour region.
13. As the pressure on the vapor is increased, eventually the path will reach the vapor:liquid
equilibrium line. The pressure holds constant for a while until all the vapour is converted to
liquid, which occupies much less volume than the vapour. Hence, the isotherm for this region is
a straight vertical line.
14. In this region, we are compressing the liquid. Since liquids are not very compressible, a large
change in pressure results in only a small change in volume; hence, the isotherm can be
approximated as a horizontal line in this region.
15. In this region of the path, we are simply compressing the solid, SI. Since solids are not very
compressible, a large change in pressure results in only a small change in volume; hence, the
isotherm can be approximated as a horizontal line in this region.
16. In this region of the path, we are simply compressing the solid, SII. Since solids are not very
compressible, a large change in pressure results in only a small change in volume; hence, the
isotherm can be approximated as a horizontal line in this region.
Page 4 of 8
1720.
20
100
T(C)
43
(2) liquid
(3) solid SI
18
17
(2) liquid
19
(3)solid SI
The path of an isobaric (constant pressure) process is a horizontal straight line on the PT diagram;
in this case at P = 1 atm. Since this is a heating curve, the path is towards higher temperature; i.e.
from left to right.
17. With initial conditions of P = 1 atm and T ~ 20 C, the phenol will all be in the SI solid state.
Over this first region of the path we are simply heating the SI phenol, so the temperature rises
linearly (in all cases in this question, we are assuming that the heat capacities of phenol in its
various forms are not functions of temperature).
18. When the temperature of the SI phenol reaches 43 C, the SI : liquid equilibrium line is reached.
At this point both SI and liquid will be in equilibrium. If the temperature is increased by a very
small amount, all of the SI solid will smoothly melt. The heat entering the system is used to bring
about the endothermic SI liquid transition, so the temperature of the system remains constant
during the phase change. It remains constant until all the SI is converted to liquid.
19. In this region, we are simply heating the liquid phenol and the temperature increases linearly.
20. When the temperature reaches 100 C, the system will be at the liquid:vapor equilibrium line. At
this point liquid and vapor will be in equilibrium. If the temperature is increased a very small
amount, all of the liquid will be converted to vapor. The heat entering the system is used in the
endothermic liquid vapor transition, so the temperature remains constant during the phase
change. It remains constant until all the liquid is converted to vapour. After all of the liquid has
been converted to vapor, the temperature will rise again.
Page 5 of 8
21.
T [K]
373
L
L
273
S
223
Time
2224,27.
Page 6 of 8
solid II
CP
A
P
[atm]
solid III
TP
liquid
B
TP
solid I
TP
vapour
T [K]
33. Liquid
Page 7 of 8
34.
35. CH3CH2CH3 has the smallest intermolecular forces. Recall that the intermolecular forces of the
liquid must be overcome for molecules to go from the liquid to the gas phase. The smaller these
intermolecular forces, the more molecules will be in the gas phase and thus the higher the vapor
pressure. CH3CH2OH can have hydrogen bonding and thus it has very strong intermolecular forces
(and hence low vapor pressure). CH3CH2CH2Cl and CH3OCH3 have dipole-dipole interactions (they
are polar molecules) and thus have stronger intermolecular forces than CH3CH2CH3 and
CH3CH2CH2CH3 (nonpolar molecules). While CH3CH2CH3 and CH3CH2CH2CH3 are both nonpolar
molecules and have only weak London (dispersion) forces as intermolecular forces,
CH3CH2CH2CH3 has stronger London interactions than CH3CH2CH3 because it has a higher
molecular weight and contains more electrons.
36. Vapor pressure depends on the number of gaseous molecules present. At higher temperatures, a
greater proportion of the molecules present will have sufficient kinetic energy to be in the gas phase.
37. C4H10 has the weakest intermolecular forces of the molecules in this question because it has the
smallest molecular weight. Thus, it has the highest vapor pressure.
38. Something with strong intermolecular forces would be expected to have a high boiling point, low
vapour pressure, high critical temperature, high viscosity, and high heat of vaporization.
39. CH3CH2CH2F has the highest vapor pressure because it has the weakest intermolecular forces of the
molecules in this question. CH3CH2CH2F has dipole-dipole intermolecular forces, but the other
molecules can have intermolecular hydrogen bonding, a stronger interaction.
Page 8 of 8
40. H2O undergoes hydrogen bonding (H2S and H2Se do not because S and Se are not electronegative
enough) and therefore has the strongest intermolecular forces and lowest vapor pressure.
41. The lower the strength of the intermolecular forces, the higher the vapor pressure. (CH3CH2)2O
doesnt have particularly high intermolecular forces (dipole-dipole interactions occur, but no
hydrogen bonding), so its vapor pressure is high at 25 C.
42. The smaller the intermolecular forces in the liquid, the more readily it will become vapor and thus
the lower its boiling point. CH4 has the weakest intermolecular forces of the molecules in this
question. C2H6 and C3H8 have higher molecular weights than CH4 and hence greater intermolecular
forces. CH3Cl has strong dipole-dipole intermolecular interactions in the liquid state while CH3OH
has very strong hydrogen bonding intermolecular interactions. CH4 is not capable of dipole-dipole
interactions or hydrogen bonding.
Page 1 of 5
CHEMISTRY 123
Problem Set #2
Thermodynamics
1. Given the enthalpy changes at a certain temperature for reactions (a) and (b), calculate the enthalpy
change for reaction (c). Is reaction (c) endothermic or exothermic at this temperature?
(a) 3H2(g) + N2(g) 2NH3(g)
(b) 2H2(g) + O2(g) 2H2O(g)
(c) 4NH3(g) + 3O2(g) 2N2(g) + 6H2O
H = 92.4 kJ mol1
H = 483 kJ mol1
2. Given the following data, evaluate the standard enthalpy of formation of ICl(g) (in kJ mol1).
Cl2(g) 2Cl(g)
I2(g) 2I(g)
ICl(g) I(g) + Cl(g)
Hsublimation of I2(s)
(1) 244.5
(2) 244.5
(3) 211.2
H = 242.0 kJ mol1
H = 151.0 kJ mol1
H = 211.2 kJ mol1
Hsub = 63.7 kJ mol1
(4) 17.1
(5) 17.1
3. The standard enthalpies of formation of CO2(g) and H2O(l) are 393.5 kJ mol1 and 285.8 kJ mol1
at 298 K, repectively. The heat of combustion of liquid pentane, C5H12(l), according to the following
equation is
C5H12(l) + 8O2(g) 5CO2(g) + 6H2O(l)
H = 3536 kJ
(3) 25.33
(4) +25.33
(5) +26.95
Page 2 of 5
(3) 121.5
(4) 121.5
(5) 138.1
(3) 46.71
(4) 46.71
(5) 0
9. If S of CO2(g) is 197.7 J K1 mol1 at 78 C, the standard entropy of solid CO2 is (in J K1):
(1) 67.70
(2) 67.70
(3) 327.7
(4) 0
(5) 130.0
10. At 279 K and 1 atm pressure, pure benzene crystallizes reversibly with an entropy change of
35.66 J mol1 K1. What is the molar heat of fusion of benzene (in kJ mol1) at its melting point?
1113. Consider the following processes at constant T and P:
Process
(1)
(2)
(3)
(4)
H
positive
positive
negative
negative
S
positive
negative
positive
negative
Answer the following questions, using the process numbers as the answer choices:
11. Which processes are ALWAYS spontaneous?
12. Which processes can be both spontaneous or non-spontaneous (i.e. the spontaneity depends
on the temperature)?
13. Which processes are NEVER spontaneous?
1418. You are given the following data at 298 K:
Ag(s)
Hf (kJ mol1)
S (J K1 mol1)
42.6
H2S(g)
20.5
206
O2(g)
Ag2S(s)
205
H2O(g)
242
189
(3) 64
(4) 285.5
(5) 728.5
(3) 145.6
(4) 145.2
(5) 383.6
(3) 43302
(4) 75300
(5) 35.6
Page 3 of 5
(4) 5.25
18. If the reaction were to occur at a higher temperature, more Ag2S(s) would be formed.
(1) True
(2) False
19. For the reaction Cl2(g) 2Cl(g), S is likely to be:
(1) positive
(2) zero
(3) negative
20. For the reaction,
N2(g) + O2(g) NO(g),
K = 1.11 102 at 1800 K, and 2.02 102 at 2000 K. The enthalpy of reaction at 2000 K is nearest
to (in kJ):
(1) 89.6
(2) 90.3
(3) 90.3
(4) 89.6
(5) 0.0896
21. Consider the following data (values are tabulated at 25 C and 1 atm pressure):
1
Hf(kJ mol )
Gf(kJ mol1)
S (J mol1K1)
NO(g)
+90.39
+86.5
O3(g)
+142.1
+163.0
NO2(g)
+33.9
+51.8
SO2(g)
296.8
O2(g)
0.0
SO3(g)
394.6
+248.3
+204.8
+255.8
C(s,graphite)
0
5.68
H2(g)
0
130.46
C3H8(g)
103.75
269.65
C2H2(g)
226.51
200.64
(a) Calculate the enthalpies, entropies, and free energies of formation of (i) propane and (ii)
acetylene from graphite and hydrogen.
(b) Calculate the equilibrium constants at 25 C for the reactions of graphite and hydrogen to form
propane and to form acetylene.
(c) From the results of (a) and (b) decide whether either of these processes is thermodynamically
feasible, and, if so, discuss what other factors would be involved in making them practical.
Page 4 of 5
23. Dinitrogen tetroxide, N2O4, dissociates reversibly into nitrogen dioxide, NO2, according to the
following reaction:
N2O4(g) 2NO2(g)
Some thermodynamic data for these compounds at 25 C are as follows:
Compound
N2O4
NO2
Hf (kJ mol1)
9.66
33.15
S (J mol1 K1)
303.9
240.4
(a) Calculate the standard free energy change, G, at 25 C for the above reaction.
(b) Calculate the equilibrium constant for the reaction at 25 C.
(c) At what temperature will the equilibrium constant for the reaction be equal to one? (Assume H
and S do not vary with temperature.)
(d) Calculate G for one mole of reaction if each gas were at 100 atmospheres partial pressure
(assume ideal behaviour).
24. Assume that all gases are ideal. For ideal gases, PV = nRT, and R = 8.314 J K1 mol1.
One possible way to make dinitrogen trioxide (N2O3) is through the following reaction:
NO(g) + NO2(g) N2O3(g)
At 298.15 K, the basic thermodynamic quantities are given below:
Substance
NO(g)
NO2(g)
N2O3(g)
Hf (kJ mol1)
91.3
33.2
82.8
S (J mol1 K1)
210.8
240.1
314.6
Gf (kJ mol1)
87.6
51.3
(a)
(b)
(c)
(d)
(e)
What is the heat of reaction under constant pressure at 298.15 K under standard conditions?
Calculate S, E, and G for this reaction at 298.15 K?
Evaluate the standard Gibbs free energy of formation, Gf, of N2O3(g) at 298.15 K.
Evaluate the equilibrium constant, K, at 298.15 K.
Write an expression for the equilibrium constant in terms of activities and in terms of partial
pressures.
(f) Could this reaction be used to mass produce N2O3 at 298.15 K? Give reasoning for your answer.
(g) Will increasing the temperature favour the production of N2O3? Give reasoning for your answer.
(h) If a chemical factory operating under standard conditions is built in a desert near the equator in
Australia, where the temperature stays above 35 C during the entire year, will N2O3 be produced
spontaneously by using this reaction? Assume that S and H do not change with the
temperature. Give reasoning for your answer.
25. The standard free energy change (G) for the hydrogenation of ethylene, shown below, is 101 kJ
at 25 C. Assume all gases are ideal; PV = nRT.
CH2=CH2(g) + H2(g) CH3CH3(g)
Page 5 of 5
(a) By inspection of the above reaction, predict the sign of the standard entropy change (S) for
this reaction at 25 C:
(1) negative
(2) positive
(3) zero
(4) cannot be determined from the given data
(b) The above reaction is:
(1) endothermic (2) exothermic (3) neither
TiCl4(g)
763.2
H2O(g)
241.8
TiO2(s)
944.7
HCl(g)
92.3
This reaction is carried out at 25 C. Assume all gases are ideal (PV = nRT).
(a)
(b)
(c)
(d)
(e)
(f)
(g)
Calculate H
Calculate G
Calculate E
Calculate S
Calculate K for this reaction at 100 C. What assumptions have you made in your calculation?
Write the expression for K in terms of activities.
At constant temperature, if 0.3 atm HCl(g) are added to the system after equilibrium is reached,
K will:
(1) increase (2) decrease (3) stay the same (4) cannot be determined from the given data
Give reasoning for your answer.
Page 1 of 11
CHEMISTRY 123
1.
Thermodynamics
(c)
Hc = 2Ha + 3Hb
= 2(92.4) + 3(483)
= 1264.2 kJ
2.
1
= +17.15 kJ mol
Note: (1) Hesss Law has been used: the total H is the sum of the individual H.
(2) When a reaction is multiplied by a constant (e.g. ) the H is multiplied by that
constant.
(3) Reversing the reaction (e.g. the third reaction listed in the question has been reversed
above to get the answer) changes the sign of H. This is equivalent to multiplying the
reaction by the constant 1.
3.
Page 2 of 11
H = 1103.4 kJ
6.
7.
S =
8.
Page 3 of 11
9.
10.
S =
q rev H
=
T
T
H = TS
(note: G = H TS = 0)
= 279 K (35.66 103 kJ mol1 K1)
= 9.95 kJ mol1
Therefore, for C6H6 (s) C6H6 (l), H = +9.95 kJ mol1
11-13. 11: The answer is (3)
12. The answer is (1, 4)
13. The answer is (2)
(1)
(2)
(3)
(4)
G = H T S
+,
+
+ +
+
+
+
+ +
,+
15.
Page 4 of 11
17.
18.
19.
20.
H S
+
RT1
R
ln K1 ln K2 =
ln K2 =
H 1
1
R T2 T1
H S
+
RT2
R
Page 5 of 11
K
ln 1
K2
H 1
1
=
R T2 T1
K
R ln 1
K2
H =
1
1
T2 T1
1.11 10 2
1 kJ
ln
2
1000 J
2.02 10
1
1
2000 K 1800 K
8.314 J mol 1 K 1
=
= 89.6 kJ mol1
21.(a) NO(g) + O3(g) NO2(g) + O2(g)
G = +51.8 + 0 86.5 163.0 = 197.7 kJ
H = +33.9 + 0 90.39 142.1 = 198.5 kJ
G = H TS
H G
T
( 198.5) ( 197.7)
=
298
= 0.00299 kJ K 1
S =
= 3.0 J K 1
G = RT lnK
G
RT
( 197.7 103 )
=
(8.314)( 298)
= +79.8
ln K =
K = 4.5 1034
(b)
Page 6 of 11
At 25 C (298 K):
G = H TS
= 97.8 298(94.9 103) = 69.5 kJ
G
RT
( 69.5 103 )
=
(8.314)( 298)
= +28.05
ln K =
K = 1.52 1012
At 327 C (600 K):
G = H TS
= 97.8 600(94.9 103) = 40.86 kJ
G
RT
( 40.86 10 3 )
=
(8.314)(600)
= +8.19
ln K =
K = 3.6 103
22.(a) (i) 3C(s) + 4H2(g) C3H8(g)
H = 103.75 kJ mol1
S = +269.65 3(5.68) 4(130.46)
= 269.23 J K1 mol1
G = H TS
= 103.75 298(269.23 103)
= 23.52 kJ mol1
(ii) 2C(s) + H2(g) C2H2(g)
H = +226.51 kJ mol1
S = +200.64 2(5.68) (130.46)
= +58.82 J K1 mol1
G = H TS
= +226.51 298(58.82 103)
= +208.98 kJ mol1
Page 7 of 11
G = RT lnK
G
ln K =
RT
( +3.92 10 3 )
=
(8.314)( 298)
= 1.58
K = 0.205
(c)
K = 1, lnK = 0, G = RT lnK = 0
Also, G = H TS = 0
Page 8 of 11
H
S
56.64 10 3 J
=
176.9 J K 1
= 320 K
T=
(d)
G = G + RT ln Q
= G + RT ln
2
PNO
2
PN 2O4
(100) 2
100
= +3.92 + 11.41
= 15.3 kJ
24.(a) qp = H
H = molesHf(products) molesHf(reactants)
= 82.8 (91.3 + 33.2)
= 41.7 kJ
(b)
S = molesS(products) molesS(reactants)
= 314.6 (210.8 + 240.1) = 136.3 J K1
G = H TS
= 41.7 298.15 (136.3 103) = 1.1 kJ
E = H (PV)
= H (nRT)
= H (n)RT
= 41.7 (1) 8.314 298.15 103 = 39.2 kJ
(c)
G = molesGf(products) molesGf(reactants)
1.1 = Gf(N2O3) (87.6 + 51.3)
Gf(N2O3) = 137.8 kJ mol1
(d)
G = RT lnK
lnK = G/(RT)
lnK = (1.1)/(8.314 298.15 103) 0.44
K e0.44 1.6
(e)
PN2O3(g)
aN2O3(g)
K =
PNO(g)PNO2(g)
aNO(g)aNO2(g)
Page 9 of 11
(f)
(g)
No.
H = 41.7 kJ < 0
Decreasing T favours exothermic reaction.
(h)
(c)
Page 10 of 11
(d)
aC2H6(g)
Q =
aC2H4(g)aH2(g)
1
PC2H6(g)
= = 1
11
PC2H4(g)PH2(g)
(e)
G = G + RT lnQ
= G + RT ln1 = G = 101 kJ
(f)
G = RT lnK
= 8.314 103 298.15 ln(1.551015) = 86.7 kJ
(c)
H = E + (PV)
(ignoring volume change of solid)
E = H (PV)
(assuming ideal gas)
= H (nRT)
(at constant T)
= H (n)RT
= 67.1 (43) 8.314 298.15 103 = 69.6 kJ
(d)
G = H TS
H G
S =
T
67.1 (86.7)
= = 0.0657 kJ K1 = 65.7 J K1
298.15
(e)
Page 11 of 11
aTiO2(s)a4HCl(g)
K =
aTiCl4(g)a2H2O(g)
(g)
Page 1 of 2
CHEMISTRY 123
1.
Problem Set #3
At 1000 K, it is found that an equilibrium mixture consists of H2S(g), H2(g), and S2(g) at partial
pressures of 41 atm, 8.2 atm, and 33 atm, respectively. The equation is:
2H2S(g) 2H2(g) + S2(g)
K for the equilibrium is:
(1) 0.13
(2) 0.76
27.
(3) 1.3
(4) 2.6
(5) 6.6
A sample initially containing 0.84 mole PCl5 and 0.18 mole PCl3 is mixed in a 10 L flask at
340 K and allowed to come to equilibrium according to
PCl5(g) PCl3(g) + Cl2(g)
At equilibrium, there are 0.72 moles of PCl5.
2.
3.
4.
5.
89.
(4) 1.4
(5) 7.2
6.
If the number of moles of PCl3 increases when the temperature increases the reaction is:
(1) exothermic as written
(2) endothermic as written
7.
If the flask was expanded to 20 L at constant temperature, the number of moles of PCl5 at
new equilibrium would:
(1) increase
(2) decrease
(3) stay the same
A 20.0 g sample of BaO2 is heated at 794 C in a closed evacuated flask of volume 3.00 L.
It decomposes according to:
BaO2(s) BaO(s) + O2(g)
K for the reaction is 0.71. The volume of the solids can be neglected.
8.
9.
Page 2 of 2
10.
11.
At 298 K, the value of the equilibrium constant is 2.0 1012 for the reaction,
2NO(g) + O2(g) 2NO2(g)
In a particular equilibrium mixture of NO, NO2, and O2 at 298 K, the number of molecules of
NO2 equals the number of molecules of NO. What is the pressure of O2 in the mixture?
12.
13.
Five grams of ammonium hydrosulphide, NH4HS, are placed in a one litre vessel and heated at
24 C. The final pressure attained is 0.618 atm.
(a)
(b)
If 50 g of NH4HS are placed in a one litre flask, what is the final pressure at 24 C?
(c)
If 0.078 g of ammonia and 5.0 g of NH4HS are initially present in a one litre flask, what
are the final pressures of ammonia and hydrogen sulphide at equilibrium at 24 C?
Page 1 of 4
CHEMISTRY 123
0.18
+0.12
0.30
0.00
+0.12
0.12
PCl 2 =
n Cl 2 RT
V
(0.12 mol)(0.08206 L atm mol 1 K 1 )(340 K )
=
10 L
= 0.33 atm
n PCl5 RT
V
(0.72 mol)(0.08206 L atm mol 1 K 1 )(340 K )
=
10 L
= 2.01atm
PPCl3 =
n PCl3 RT
V
(0.30 mol)(0.08206 L atm mol 1 K 1 )(340 K )
=
10 L
= 0.84 atm
K=
PPCl3 PCl 2
PPCl5
(0.84)(0.33)
2.01
= 0.14
=
Page 2 of 4
PO 2 V
RT
(0.50 atm)(3.00 L)
(0.08206 L atm mol 1 K 1 )(1067 K )
= 0.017 mol
=
0.118
0.034
0.084
0.000
+0.034
0.034
0.000
+0.017
0.017
Page 3 of 4
(b) PH =
K=
2
PNO
PO2
2
PNO
= 22
P
NO
1
=
PO
2
PO2 =
P
O 2
1
1
=
= 5.0 1013 atm
12
K 2.0 10
2
PCO
PCO2
PCO = K1 K 2
= (3.9 10 2 )(1.9)
= 0.27 atm
Page 4 of 4
final moles
0.098
x
0.098 x
0
+x
x
0
+x
x
PV
0.309 atm 1.0 L
=
= 0.013 mol
RT 0.0821 L atm mol 1 K 1 298 K
Final
0.098 mol
xV/RT mol
(0.098 xV/RT) mol
NH3(g)
0.112 atm
+x atm
(0.112 + x) atm
H2S(g)
0
+x atm
x atm
Page 1 of 3
CHEMISTRY 123
Problem Set #4
Electrochemistry
Note: Refer to the table at the end for value when necessary.
1. Explain how electrochemical measurements could be used to determine the change in Gibbss
Free Energy G for the redox process:
Zn + Cu2+ Cu + Zn2+
2. Calculate the equilibrium constant at standard conditions for the reaction:
Cu(s) + Cl2(g) CuCl2(aq)
3. Calculate the G(298 K) for the following reactions based on the electrode potentials in the
table: (a) Pb(s) + ZnCO3(aq) PbCO3(aq) + Zn(s)
(b) K(s) + H2O(l) KOH(aq) + H2(g)
(c) K2S2O8(aq) + 2KI(aq) I2(s) + 2K2SO4(aq)
4. A disproportionation reaction involves a substance that is both oxidized and reduced. Is the
disproporionation reaction
(note: this is not balanced)
HClO2(aq) ClO3(aq) + HClO(aq)
spontaneous under standard conditions?
Use: ClO3 + 3H+ + 2e HClO2 + H2O
= +1.21 V
+
= +1.65 V
HClO2 + 2H + 2e HClO + H2O
5. Consider the following Galvanic cell at T = 25 C
Pt | Cr2+(0.3M), Cr3+(2.0M) || Co2+(0.2M) | Co
The overall reaction is:
2Cr2+(aq) + Co2+(aq) 2Cr3+(aq) + Co(s)
which has an equilibrium constant K = 2.79 107.
Calculate the cell potential and G for the cell reaction at these conditions.
6. A cell has the following reaction
Cu(s) + 2 Ag+(aq) Cu2+(aq) + 2 Ag(s)
Increasing the concentration of Ag+ by a factor of 10 will change the cell potential by how many
volts? The temperature is 25 C.
(1) 0.0295 V
(2) 0.059 V
(3) 10.00 V
(4) +0.059 V
(5) the cell potential is unchanged
7. For a certain redox reaction the standard cell potential ( ) is positive. Which of the following
is correct?
(1) G > 0, K > 1
(2) G > 0, K < 1
(3) G < 0, K > 1
(4) G < 0, K < 1
(5) none of the above
Page 2 of 3
= 0.913 V
Cr (aq) + 2e Cr(s)
(1) Write the overall cell reaction in the direction of spontaneous change.
(2) Calculate the standard cell potential and G.
(3) Calculate the cell potential when the concentration of Cr2+(aq) and Cr3+(aq) are both
0.001 M.
(4) Qualitatively (that is increase, decrease, or no change), what happens to the cell potential of a
cell operating under standard conditions, when some NaOH solution is added to the
compartment containing Cr(s) and Cr2+(aq)? The compound Cr(OH)2 precipitates: it is a
sparingly soluble substance. Provide a brief explanation of your choice.
(5) Given that the standard cell potential goes down on raising the temperature, what is the sign
of the enthalpy change for the cell reaction at 25 C? Provide a brief explanation of your
choice.
(6) Calculate the half-cell potential for the following half-cell reaction at 25 C:
Cr3+(aq) + 3e Cr(s)
10. Consider the galvanic cell based on the following half-cell reactions
Br2(l) + 2e 2Br(aq)
= +1.08 V
Fe3+(aq) + e Fe2+(aq)
= +0.77 V
(1) Write the overall cell reaction in the direction of spontaneous change.
(2) Calculate the standard cell potential and G.
(3) If the cell is operated with the [Fe3+] concentration set at 1.00 M and the [Fe2+] concentration
set at 1.00 104 M in the Fe2+/Fe3+ electrode, what concentration of Br is required in the
Br2/Br electrode so that Fe3+ will be spontaneously reduced?
Page 3 of 3
Page 1 of 6
CHEMISTRY 123
Electrochemistry
1. Because of the relation between G and the cell potential , one can use an electrochemical
measurement of to determine G via G = nF . For the given reaction, we must first use
the two half-cell reactions:
Cu2+(aq) + 2e Cu(s)
Zn(s) Zn2+(aq) + 2e
to determine that n = 2 mol, that is 2 mol of e are transferred for each mole of the reaction. One can
then set up a standard galvanic cell, with the species under standard conditions, i.e. 1 Molar solutions
and pure metal electrodes. Thus, we obtain G without ever measuring H or S.
2. Cu(s) + Cl2(g) CuCl2(aq)
Half-cell reactions based on the overall redox reaction:
Cu2+(aq) + 2e Cu(s)
= 0.340 V
= 1.358 V
Cl2(g) + 2e 2Cl (aq)
The standard cell potential = 1.358 0.340 = 1.018 V
G = nF = 2 mol 96500 J mol1 V1 1.018 V
= 196.5 kJ (for the reaction as written)
Because: G = RT lnK
lnK = G / (RT) = (196474 J) / (8.134 J mol1 K1 298 K) = 79.30
K = e79.30 = 2.75 1034
K is huge, much larger than 1, so the equilibrium lies far to the right (as written). The reaction
essentially goes to completion and we can neglect the reverse reaction.
3. a) Pb(s) + ZnCO3(aq) PbCO3(aq) + Zn(s)
Half-cell reactions based on the overall redox reaction:
Zn2+(aq) + 2e Zn(s)
Pb(s) Pb2+(aq) + 2e
Refer to the table at the end, we get
Zn2+(aq) + 2e Zn(s)
Pb2+(aq) + 2e Pb(s)
= 0.763 V
= 0.125 V
Page 2 of 6
= 0.828 V
= 2.924 V
= 2.01 V
= 0.535 V
oxidization
reduction
Page 3 of 6
Thus,
= RT/(nF) lnQ
= 0.22 V 1 mol 8.314 J mol1 K1 298 K / (2 mol 96500 J mol1 V1) ln222.22
= 0.15 V
6. The answer is (4).
= RT/(nF) lnQ
0.0258 V
=
lnQ
n
=
[Cu 2+ ]
0.0258 V
0.0258 V
lnQ =
ln
+ 2
n
2
[Ag ]
f i =
[Cu 2+ ]f
0.0258 V
ln
+ 2
2
[Ag ]f
[Cu 2+ ]i
0.0258 V
+
ln
+ 2
2
[Ag ]i
[Cu 2+ ]f
0.0258 V
ln
+ 2
2
[Ag ]f
0.0258 V
[Cu 2+ ]i
+
ln
+ 2
2
[Ag ]i
[Cu 2+ ]f
0.0258 V
ln
+ 2
2
[Ag ]f
0.0258 V
[Ag + ]i2
ln
2+
2
[Cu ]i
0.0258 V
2
[Cu 2+ ]f
ln
+ 2
[Ag ]f
[Ag + ]i2
+ ln
2+
[Cu ]i
ln
=
2+
+ 2
2
[Cu
]
[Ag
]
i
f
[Ag + ]i2
0.0258 V
ln
=
+ 2
2
[Ag
]
f
12
0.0258 V
ln 2
=
2
10
0.0258 V
ln 10 2 = 0.059 V
2
Page 4 of 6
8. This half-cell reaction is a sum of the two half-cell reactions provided above.
Fe2+(aq) + 2e Fe(s)
1 = 0.440 V
(1)
3+
2+
+) Fe (aq) + e Fe (aq)
2 = +0.771 V
(2)
Fe3+(aq) + 3e Fe(s)
3 1 + 2 ??? (3)
The available data can be summarized in the following table:
n1 = 2
n2 = 1
n3 = 3
1 = 0.440 V
2 = +0.771 V
3 = ???
3 = 1 + 2
3 = 0.036 V
G1 = n1F1 = 2F1
G2 = n2F2 = F2
G3 = n3F3 = 3F3
G3 = G1 + G2
3F3 = 2F1 F2
+)
Cr(s) Cr (aq) + 2e
= +0.913 V
K1
K2
1
2
Page 5 of 6
()
+) Cr (aq) + 2e Cr(s)
2 = 0.913 V
(2)
Cr3+(aq) + 3e Cr(s)
3 1 + 2 ??? (3)
The available data can be summarized in the following table:
n1 = 1
n2 = 2
n3 = 3
1 = 0.407 V
2 = 0.913 V
3 = ???
3 = 1 + 2
3 = 0.744 V
G1 = n1F1 = F1
G2 = n2F2 = 2F2
G3 = n3F3 = 3F3
G3 = G1 + G2
3F3 = F1 2F2
+) 2 { Fe (aq) Fe (aq) + e }
= 0.77 V
Page 6 of 6
For Fe3+ to be spontaneously reduced, < 0: the reverse reaction in part (1).
= 0.31 0.01284 lnQ < 0
lnQ > 0.31/0.01284 = 24.14
Q > 3.05 1010
Q = 108 [Br]2 > 3.05 1010
[Br]2 > 3.05 102
[Br] > 17.46 M
The Br concentration must be bigger than 17.46 M.
Page 1 of 3
CHEMISTRY 123
Problem Set #5
(5) HCN
2.
3.
Kw for water at normal body temperature, 37 C, is 2.42 1014. What is the pH for a neutral
solution at this temperature?
(1) 0
(2) 6.8
(3) 7.0
(4) 7.2
(5) 14
4.
(5) 12.1
5.
The acid ionization constant for HSO3 is 6.24 108; therefore the base ionization constant for
SO32 is
(1) 1.7 102
(2) 2.5 104
(3) 3.1 108
(4) 1.6 107
(5) 1.6 107
6.
(5) 12.1
7.
What is the pH of a solution of 0.300 mole of acetic acid (Ka = 1.80 105) and 1.50 moles of
sodium acetate in 1.00 liter of water?
(1) 0.52
(2) 4.05
(3) 5.44
(4) 7.00
(5) 8.56
8.
When 10 mL of 5 M HCl are added to the solution from question 7, the change in pH is
(1) +0.08
(2) 0.08
(3) +0.18
(4) 0.18
(5) +0.28
9.
An equimolar solution of chloroacetic acid (Ka = 1.4 103) and its potassium salt in water has an
approximate pH of
(1) 1.4
(2) 2.9
(3) 7.0
(4) 8.4
(5) 9.9
12. The pH of a 0.158 M solution of NH3 is 11.22. What is the percent dissociation of NH3 in this
solution?
(1) 0.0105%
(2) 1.05%
(3) 10.5%
(4) 0.166%
(5) 9.45%
Page 2 of 3
13. Given Ka(HCN) = 4.0 1010; Ka(CH3COOH) = 1.8 105, then a 1 M solution of sodium acetate
is more basic than a 1 M solution of sodium cyanide.
(1) true
(2) false
14. The pH of a 5.0 108 M HCl solution is
(1) 6.72
(2) 6.89
(3) 7.00
(4) 7.30
(5) 7.51
(4) 7.21
(5) 7.47
(5) 4.46
17. The addition of sodium acetate to a solution of acetic acid in water will
(1) reduce the pH of the solution.
(2) increase the degree of ionization of the acetic acid.
(3) increase the H+ concentration in the solution.
(4) cause Ka for acetic acid to decrease.
(5) represse the ionization of acetic acid.
18. A solution contains 0.20 mol per liter of NH3 and 0.10 mol per liter of NH4Cl. What is the OH ion
concentration in this solution? Kb for ammonia is 1.8 105?
(1) 1.8 103 M
(2) 3.6 105 M
(3) 9.0 103 M
(4) 3.6 106 M
(5) 6.0 103 M
19. Hypochlorous acid (HClO) is a weak acid. It ionizes slightly in water to produce hydrogen ions and
hypochlorite ions (ClO). Which one of the following substances could be used with hypochlorous
acid to make a buffer solution?
(1) NaClO4
(2) KaClO
(3) KNO3
(4) NaCl
(5) HClO4
20. What is the pH of a buffer solution that contains 0.20 M formic acid and 0.20 M sodium formate?
The Ka of monoprotic formic acid is 6.0 104.
(1) 4.96
(2) 2.34
(3) 4.56
(4) 3.22
(5) 1.96
21. What mass of sodium hydroxide should be added to 100 mL of a 0.0100 M acetic acid solution in
order that the solution should have a pH of 4.74? Ka for acetic acid is 1.8 105. Assume that the
volume does not change when this sodium hydroxide is added.
(3) 8.00 mg
(4) 20.0 mg
(5) 80 mg
(2) 1.0 103 g
(1) 5.0 104 g
22. A buffer solution is prepared from the weak base ammonia and its conjugate acid such that the
concentration of the base is exactly ten times the concentration of its conjugate acid. What is the pH
of this buffer solution if Kb for ammonia is 1.8 105?
(1) 3.74
(2) 10.26
(3) 8.26
(4) 5.74
(5) 9.26
23. Given 100.0 mL of a buffer that is 0.5 M in HOCl and 0.40 M in NaOCl, what is the pH after 10.0
mL of 1.0 M NaOH has been added? (Ka for HOCl is 3.5 108)
(1) 6.45
(2) 6.64
(3) 7.36
(4) 7.45
(5) 7.55
Page 3 of 3
24. How many millimoles of HCl must be added to 100 mL of a 0.100 M solution of methylamine
(pKb = 3.36) to give a buffer having a pH of 10.0? Assume no volume changes.
(1) 8.1
(2) 18.7
(3) 20.0
(4) 6.1
(5) 12.7
25. Calculate the pH of pure water at 45 C (Kw = 4.20 1014 at 45 C). Is this solution acidic, neutral,
or basic? Explain your answer.
26. To 200 mL of 0.100 M benzoic acid (C6H5COOH) solution is added 110 mL of 0.100 M NaOH
solution. Calculate the pH for the new solution (Ka for benzoic acid = 6.3 105). If 2.00 103
mol of HCl are added to the above solution and equilibrium is reached. Calculate the pH of the
resulting solution.
Page 1 of 10
CHEMISTRY 123
1. 2
2. 4
3. 2
4. 4
5. 5
6. 2
7. 3
8. 2
9. 2
10. 3
11. 2,4
12. 2
13. 2
14. 2
15. 4
16. 5
Detailed Solutions
1. HClO4 is the strongest acid. Hence, it has the highest dissociation constant.
2. Note: throughout this problem set, H+ and H3O+ are used interchangeably.
pH = log[H+]
3.75 = log[H+]
[H+] = 1.8 104 M.
3. H2O(l) H+(aq) + OH(aq)
x
x
[BH + ][OH ]
Kb =
= 1.8 105
[B]
( x )( x )
= 1.8 105
0.20 x
Assume x << 0.20 M. We expect this to be a reasonable assumption because the value of Kb is
relatively small. Therefore, 0.20 x 0.20 and we have:
x2
= 1.8 105
0.20
x = [OH] = 1.9 103 M
pOH = log(1.9 103) = 2.72
Page 2 of 10
pH + pOH = 14
pH = 14 2.72 = 11.28.
Check the assumption:
1.9 10 3 M
x
100% =
100% = 0.95%
0.20 M
0.20 M
x < 1% of 0.20 M, therefore the assumption is OK.
5. Kw = KaKb
1 1014 = (6.24 108) Kb
Kb = 1.6 107
6. Kw = KaKb
1 1014 = Ka (1.8 105)
Ka = 5.6 1010
NH4+
0.40 x
Ka =
[ NH 3 ][H 3 O + ]
= 5.6 1010
+
[ NH 4 ]
( x )( x )
= 5.6 1010
0.40 x
Assume that x << 0.40 M. We expect this to be a reasonable assumption because the value of Ka is
relatively small. Therefore, 0.40 x 0.40 and we have:
x2
= 5.6 1010
0.40
x = [H3O+] = 1.5 105 M
pH = log(H3O+) = log(1.5 105) = 4.8.
Check the assumption:
1.5 10 5 M
x
100% =
100% = 0.00375%
0.40 M
0.40 M
x < 1% of 0.40 M, therefore the assumption is OK.
Page 3 of 10
7. [H3O+] = K a
[acid]
[base]
[base]
[H+] =
(Note: the total volume is now 1.010 L since 10 mL of acid has been added.)
To calculate the new pH:
Because: [H3O+] = K a
[acid]
[base]
[base]
1.44
= log(1.80 105) + log
pH = pKa + log
= 5.36
0.35
[acid]
pH = 5.36 5.44 = 0.08
9. [H3O+] = K a
[acid]
[base]
[base]
Page 4 of 10
10. The strongest base has the highest Kb. Since pKb = log Kb, the highest Kb (greatest base strength)
results in the smallest pKb: Kb(acetate ion) < Kb(N2H4) < Kb(NH3) < Kb(CN).
11. (1) KClO4 K+(aq) + ClO4(aq)
ClO4 is the weak conjugate base of the strong acid HClO4. Because it is weak, it does not react
with H2O appreciably. All the H+ and OH in solution are therefore from water dissociation only.
The resulting solution is neutral.
(2) NaHSO4 Na+(aq) + HSO4 (aq)
HSO4 + H2O H3O+ (aq) + SO42(aq)
HSO4 is a strong acid. It reacts with H2O to give H3O+ and the resulting solution is acidic.
CN is the strong conjugate base of the weak acid HCN. It reacts with H2O to give OH and the
resulting solution is basic.
NH4+ is the strong conjugate acid of the weak base NH3. It reacts with H2O to give H3O+ and the
resulting solution is acidic.
CO32 is the strong conjugate base of the weak acid HCO3. It reacts with H2O to give OH and
the resulting solution is basic.
moles NH 3 dissociated
1.66 10 3 mol
100% =
100% = 1.05%
initial moles NH 3
0.158 mol
Page 5 of 10
Page 6 of 10
CH3CO2H
16.
1.0 104 M x
CH3CO2(aq)
H+(aq)
x
[CH 3 CO 2 ][H + ]
Ka =
[CH 3 CO 2 H]
1.82 105 =
( x )( x )
1.0 10 4 x
However, when a salt containing the acetate ion is added, the [CH3COO] is larger than x. For
example, sodium acetate completely dissociated when added to the solution. If the initial
concentration of NaCH3COO is B, then the concentration of the CH3COO produced from the salt
dissociating is also B:
NaCH3COO(s) CH3COO(aq) + Na+(aq)
B
B
This is a case of the common ion effect. The CH3COO comes from two sources (acid dissociation
and salt dissociation) and the total [CH3COO] is B + x. Now the form for Ka is:
Ka =
Page 7 of 10
Since [CH3COO] increases when it comes from two sources, then [H+] must decrease so that
Ka remains constant: if the concentration of one ion involved in the acetic acid equilibrium goes up,
the concentration of the other ion must go down. Therefore, [H+] = x is less, i.e. the degree of
ionization of the acetic acid is repressed. In addition, the pH wil be higher since [H+] is lowered.
18.
(0.10 + x )( x )
0.20 x
(0.10)( x )
0.20
[base]
[acid]
[acid]
Page 8 of 10
[acid]
[base]
[base]
0.20
= log(6.0 104) + log
So, pH = pKa + log
= 3.22
0.20
[acid]
21. First react base with acid. Assume all base added reacts completely and is used up.
Let y = [OH] added (since we assume no volume change, we can use concentration here instead of
#moles)
CH3COOH + OH CH3COO + H2O
0.0100
y
0
0
y
y
+y
+y
0.0100y 0
y
y
initial conc.
change
final conc.
[H3O+] = K a
[acid]
[base]
[base]
pH = pKa + log
[acid]
y
4.74 = log (1.8 105) + log
0.0100 y
y
log
= 0
0.0100 y
= 1
0.0100 y
[base]
[acid]
[acid]
1
= log(1.8 105) + log = 3.74
So, pOH = pKb + log
10
[base]
pH = 14 pOH = 10.26
Page 9 of 10
initial moles
change
final moles
[HOCl] =
[H3O+] = K a
[acid]
[base]
0.455 M
[base]
= 7.55
= log (3.5 108) + log
So, pH = pKa + log
0
.
364
M
[acid]
24. CH3NH2 = methylamine. (Note: we do not need to know the formula to do the question! One could
simply assume that A is methylamine and HA+ is its conjugate acid.)
pOH = 14 pH = 14 10.0 = 4.0
[OH] = K b
[base]
[acid]
[acid]
Page 10 of 10
Let x = moles of HCl added. Assume all the added HCl reacts with CH3NH2 (the weak conjugate
base) to produce CH3NH3+ (the weak acid):
initial moles
change
final moles
x
= 4.365
0.01 x
x = 0.0081 mol = 8.1 mmol
25. [OH][H3O+] = Kw
[OH] = [H3O+] for pure water
[H3O+]2 = 4.20 1014
[H3O+] = 2.049 107
pH = log10[H3O+] = 6.69
This solution is neutral, as [OH] = [H3O+] (despite the pH being below 7).
26. In the beginning, moles of HA = 0.200L 0.100M = 0.020,
moles of OH = 0.110L 0.100M = 0.011
At equilibrium, moles of HA = 0.020 0.011 = 0.009, moles of A = 0.011
[H3O+]= Ka[HA]/[A] = 6.3 105 0.009/0.011 = 5.15 105
pH = log10[H3O+] = log10(5.15 105) = 4.29
Once more HCl is added, at new equilibrium, moles of HA = 0.009 + 0.002 = 0.011,
moles of A = 0.011 0.002 = 0.009
[H3O+] = Ka[HA]/[A] = 6.3 105 0.011/0.009 = 7.70 105
pH = log10[H3O+] = log10(7.70 105) = 4.11