UP Academic League of Chemical Engineering Students (UP ALCHEMES)

Academics Affairs Committee Review and Tutorials Program, AY 2013-2014

Chem 17 Second Exam (SAMPLE EXAM) Answer Key
I. Modified True or False
1. TRUE 6. orange light
2. 1.0 M NaOH < 0.3 M CaCl2 < 0.3 M KCl < 0.3 M 7. would occur
Na2SO4 < 1.5 M NaCl 8. cannot be prepared
3. to reverse 9. minimum
4. [Fe(H2O)5(OH)]2+ 10. lower than 7
5. Presence of pink [Co(H2O)6]2+ and blue [Co(Cl)4]2-
II. Multiple Choice
1. C 3. B 5. A 7. A 9. D 11. B 13. A 15. C
2. C 4. B 6. D 8. D 10. A 12. A 14. D
III. Problem Solving
1.
a. B – 1st endpoint, D – 2nd endpoint, F – 3rd endpoint
b. A – 1st half endpoint, C – 2nd half endpoint, E – 3rd half endpoint
c. At 1st half endpoint, pOH = pKb1. Therefore, pKb1 = 14 - 11.4 = 2.6
pK b1  pK b2
At 1st endpoint, pOH  . Therefore pK b2  2(14  9.085)  2.60  7.23
2
pK b2  pK b3
At 2nd endpoint, pOH  . Therefore pK b2  2(14  4.58)  7.23  11.61
2
20 mL  1.00 M
d. The molarity of the SAH sample (by using the first equivalence point) is  0.40 M
50 mL
0.40 M  50 mL
At the final endpoint, molarity of arsenic acid (conjugate) is  0.182 M .
50 mL  60 mL
From the pKb values, pK a  14  pK b . Thus, pKa1  2.39, pKa 2  6.77, pKa 3  11.40 .
Since the difference between pKa2 and pKa1 is large, then we can assume that contribution of H3O+ from pKa2 and pKa3 is
negligible.

H3A H2O H2A- H3O+

I 0.182 --- 0 0
C -x --- +x +x
E 0.182 - x --- x x

x2
 102.39  x   H3 O   0.02525 M  pH=-log  0.02525 M   1.60
0.182  x
0.40 M  50 mL 1.00 M  2 mL
e. Molarity of arsenic acid is  0.1786 M . Molarity of excess acid is  0.01786 M .
50 mL  62 mL 50 mL  62 mL

H3A H2O H2A- H3O+

I 0.1786 --- 0 0.01786
C -x --- +x +x
E 0.1786 - x --- x 0.01786 + x

 x  0.01786  x 
 102.39  x  0.01815 M  pH=-log  0.01786 M  0.01815 M   1.44
0.1786  x
1L 1 mol SAH 216.89 g
f. 20 mL  1.00 M     5.000 g  100%  86.76%
1000 mL 1 mol H+ 1 mol SAH
g. 1st endpoint – thymolphthalein, 2nd endpoint – bromocresol green, 3rd endpoint – thymol blue

2.
a. Note the equation for osmotic pressure:   Mtot RT . Using an ICE table we can find a formula for Mtot:

H2A H2O HA- H3O+

I c --- 0 0
C -x --- +x +x
E c-x --- x x
 HA- H2O A2- H3O+
I x --- 0 x
C -y --- +y +y
E x–y --- y x+y

Therefore, the Mtot will be   H2 A    HA     A 2     H3 O   cacid  x  x  y  y  x  y  cacid  x  y

  x2 
Since  A 2   is negligible, then M tot  c acid  x   c acid  x,  log    pK a1
RT  cacid  x 
For aminomalonic:
  1.852  10-3 M  
2
0.2655 atm
x  0.009 M = 1.852  10 M  pK a1   log 
-3   3.32
L atm  0.009 M  1.852  10-3 M 
0.08206  298.15 K  
mol K
For citraconic:
  4.713  10-3 M  
2
0.3355 atm    2.29
x  0.009 M = 4.713 10 M  pK a1   log
-3
L atm  0.009 M  4.713  10-3 M 
0.08206  298.15 K  
mol K
For diethylmalonic:
  4.978  10-3 M  
2
0.3420 atm    2.21
x  0.009 M = 4.978  10 M  pK a1   log
-3
L atm  0.009 M  4.978  10-3 M 
0.08206  298.15 K  
mol K
For iminodipropionic:
  7.972  10-4 M  
2
0.2397 atm    4.11
x  0.009 M = 7.972  10 M  pK a1   log
-4
L atm  0.009 M  7.972  10-4 M 
0.08206  298.15 K  
mol K
For maleic:
  6.013  10-3 M  
2
0.3673 atm    1.92
x  0.009 M = 6.013  10 M  pK a1   log
-3
L atm  0.009 M  6.013  10-3 M 
0.08206  298.15 K  
mol K
pK a1  pK a 2
Note that for an ampholyte, pH   pK a 2  2pH  pK a1 .
2
For aminomalonic: pK a 2  2  6.575   3.32  9.83 . For citraconic: pK a 2  2  4.220   2.29  6.15 .
For diethylmalonic: pK a 2  2  4.750   2.21  7.29 . For iminodipropionic: pK a 2  2  6.860   4.11  9.61 .
For maleic: pK a 2  2  4.075   1.92  6.23
b.
H2A H2O HA- H3O+
I 0.001 --- 0 0
C -x --- +x +x
E 0.001 - x --- x x
x2
 101.92  x   H3 O    HA    9.283  10 4 M
0.001  x initial initial

HA- H2O A2- H3O+

I x --- 0 x
C -y --- +y +y
E x–y --- y x+y
9.283  10  y   y   10
4
6.23
 assume y is very small 
9.283  10   y   10
4
6.23

9.283  10  y 
4
9.283  10  4

y   A 2-  = 5.88×10-7 M,  HA    x  y  9.277×10-4 M,  H2 A   0.001  x  7.168×10-5 M

 H3 O   x  y  9.289×10-4 M  pH   log  9.289×10-4 M   3.03
 c. pH 4.00 bufffer – iminodipropionate, pH 6.00 buffer – citraconate, pH 10.00 buffer - aminomalonate
d. millimoles buffer =  0.100 M  200 mL   20 mmol
For pH 4.00 buffer:
  HA   
 
4.00  4.11  log   0.776  H 2 A    HA    0.776  H 2 A    H 2 A   20 mmol
  H2 A  
 
 H2 A  11.26 mmol, HA    8.74 mmol
HA- H3O+ H2A H2O
I 20.00 11.26 0 ---
C -11.26 11.26 +11.26 ---
Final 8.74 0 11.26 ---

A2-
H3O+ HA- H2O
I 20.00
31.26 0 ---
C -20.00
-20.00 +20.00 ---
Final 0
11.26 20.00 ---
205.12 g 1 mL
20.00 mmol   4.1024 g Na 2 A , 31.26 mmol   20.84 mL HCl
1000 mol 1.50 mmol

For pH 6.00 buffer:

 A2  
  
6.00  6.15  log   0.708  HA     A 2    0.708  HA     HA    20 mmol
  HA   
 
 HA    11.71 mmol,  A 2    8.29 mmol
A2-
H3O+ HA- H2O
I 20.00
11.71 0 ---
C -11.71
-11.71 +11.71 ---
Final 8.29
0 11.71 ---
174.07 g 1 mL
20.00 mmol   3.4814 g Na 2 A , 11.71 mmol   7.81 mL HCl
1000 mol 1.50 mmol

For pH 10.00 buffer:

 A2  
  
10.00  9.83  log   1.479  HA     A 2    1.479  HA     HA    20 mmol
  HA  

 
 HA    8.07 mmol,  A 2    11.93 mmol
A2-
H3O+ HA- H2O
I 20.00
8.07 0 ---
C -8.07
-8.07 +8.07 ---
Final 11.93
0 8.07 ---
163.04 g 1 mL
20.00 mmol   3.2608 g Na 2 A , 8.07 mmol   5.38 mL HCl
1000 mol 1.50 mmol
3.
a. First, determine which cation precipitates first.
K sp 8.5  10 17 K sp 7.1 10 9
For AgI: I      3.4  10 15
M , for PbI 2:  I
 

    4.21 10 4 M .
 Ag   0.025  Pb2   0.04
K sp 6.5  10 4
For TlI: I      0.026 M . Thus AgI will be the first precipitate since it needs the least concentration of I - to
 Tl   0.025
precipitate. We can safely assume that Pb2+ will be the second cation to precipitate since the iodide concentration it needs to
precipitate is much smaller than what Tl+ needs.

When the number of moles of Ag reaches the number of moles of I stoichiometrically (its “equivalence point”), the equilibrium
concentration of iodide becomes Ksp  9.22  109 . Since the concentration of iodide is still small to induce precipitation of
PbI2, the second cation will precipitate after a certain volume of NaI from the “equivalence point”.
 0.025M  50 mL
Thus mL of NaI to reach equivalence point   12.5 mL . Let x be the additional volume of NaI to be added.
0.1 M
After the equivalence point of AgI precipitation some concentration of I - will be produced due to equilibrium, but the Ksp of AgI
is so small that the additional concentration of I- is considered to be negligible. Thus, the solution can be simplified by only
considering the Ksp of PbI2.

Moles of Pb 0.04 M  50 mL  2.00 mmol :

2
 0.1 M  x mL 
 Pb2   I    7.1 109  
2 2 mmol 9
   7.1 10  x  0.296 mL
 x mL  50 mL  12.5 mL  x mL  50 mL  12.5 mL 
Thus the volume of NaI to be added just before the second cation precipitates is 0.296 mL  12.5 mL  12.80 mL
b. Moles of Ag: 0.025 M  50 mL  1.25 mmol , moles of NaI: 0.1 M  12.80 mL  1.28 mmol
Use ICE table to find the concentration of [Ag+] remaining in solution:
AgI Ag+ I-
Initial moles --- 1.25 1.28
Change in moles --- -1.25 -1.25
0.0296 mmol
Final Molarity --- 0  4.723  104 M
50 mL + 12.80 mL
C --- +x +x
E --- x 4.723×10-4 + x
8.5  1017
 
4.723  104  x  x   8.5  1017 , Assume x is very small  x 
4.723  104
 1.800  1013

1.800  10 13 M
% ppt'n   100%  7.20  10 10 %  0.1% , thus precipitation is complete.
0.025 M
c. Since the precipitating agent is different, it does not mean Pb2+ will be the second cation to precipitate.
2 mmol
 Pb2     0.03185 M ,  Tl    0.025 M  50 mL  0.0199 M
new 62.80 mL   new 62.80 mL
K sp 1.6  10 5 K sp 1.7  10 4
For PbCl2: Cl      0.0224 M , for TlCl: Cl      8.54  10 3 M
 Pb 
2
0.03185  Tl 

0.0199

Thus, Tl+ will be the second cation to precipitate. At the equivalence point, Cl    1.7  104  0.01303 M , which is not
enough to enduce precipitation of PbCl2. Thus, PbCl2 will precipitate after a certain volume of NaI from the “equivalence point”.

Since the Ksp of TlCl is slightly large, we must take into account the additional concentration of Cl - produced from TlCl after the
equivalence point. Let y be the additional concentration of Cl- from TlCl.

0.025M  50 mL
Moles of Tl: 0.025 M  50 mL  1.25 mmol , volume of NaCl to reach equivalence point is   2.5 mL .
0.1 M
TlCl Tl+ Cl-
Initial moles --- 1.25 0.5 M × (x + 2.5) mL
Change in moles --- -1.25 -1.25
0.5 M  x mL
Final Molarity --- 0
62.80 mL + x mL  2.5 mL
C --- +y +y
0.5 M  x mL
E --- y y
62.80 mL + x mL  2.5 mL

0.5 M  x mL
 Tl   Cl    1.7  104   y   
 y   1.7  10 4
 x mL  62.80 mL  2.5 mL 
2
2  2 mmol  0.5 M  x mL 
 Pb2   Cl    1.6  105     y   1.6  10 5
 x mL  62.80 mL  2.5 mL   x mL  62.80 mL  2.5 mL 
0.5 M  x mL 2 mmol
Let  y  m, n:
x mL  62.80 mL  2.5 mL x mL  62.80 mL  2.5 mL
 1.7  10 
2
 ym  4
2
y2 2 mmol
   1.81 103  y  1.81 10 3 n  0.0425 
nm 2 1.6  105 n x mL  62.80 mL  2.5 mL

2
 2 mmol  0.5 M  x mL 2 mmol  5
    0.0425    1.6  10
 x mL  62.80 mL  2.5 mL  x mL  62.80 mL  2.5 mL x mL  62.80 mL  2.5 mL 
x  2.146 mL

Thus the volume of NaCl to be added just before the third cation precipitates is 2.146 mL  2.5 mL  4.65 mL

d. Based from the ICE table of TlCl, the amount of Tl+ remaining is also equal to y.
2 mmol
y   Tl    0.0425   7.319  10 3
x mL  62.80 mL  2.5 mL
7.319  10 3
% ppt'n   100%  29.28%  0.1% , thus precipitation is not complete.
0.025 M
e. Precipitation will be complete if the final concentration of cation is less than 0.1%.
2 mmol
 Pb2before

  0.0297 M   Pbfinal  0.0297 M  0.1%=2.97  10 5 M
2

67.44 mL
Let x be the mL of Na2SO4 needed.

PbSO4 Pb2+ SO42-

Initial moles --- 2 0.5x
Change in moles --- -2 -2
0.5x  2 mmol
Final Molarity --- 0
67.44 mL + x
C --- +2.97×10-5 +2.97×10-5
0.5x  2 mmol
E --- 2.97×10-5  2.97  105
67.44 mL + x
 0.5x  2 mmol 
  2.97  10 5   2.97  10 5   1.6  10 8  x  4.07 mL
 67.44 mL + x 
f. The fourth cation, based on the given Kf and Ksp data, is Fe3+. Find the concentration of [Fe(EDTA)]- and NH3 and the overall
equilibrium. We can safely assume that  Fe3    Fe(EDTA)  since the Kf value is very large.


 

Since the number of moles of Fe3+ is equal to the moles of EDTA4- and the Kf value is large, we can assume that the remaining
EDTA4- in equilibrium is negligible.

0.02 M  50 mL 3.0 M  15 mL
 Fe(EDTA)    0.0114 M,  NH3    0.514 M
   67.44  4.07  1.00  15  mL  67.44  4.07  1.00  15  mL

Fe  EDTA  Fe3  EDTA 4 
Fe3  3OH Fe  OH 3(s)
3NH3  3H2 O 3OH  3NH4

 Fe  EDTA   3NH3  3H2 O Fe  OH 3(s)  3NH4  EDTA 4 

[Fe(EDTA)]- 3NH3 H2O Fe(OH)3 3NH4+ EDTA4-

I 0.0114 0.514 --- --- 0 0
C -x -3x --- --- +3x +x
E 0.0114 - x 0.514 – 3x --- --- 3x x
 3x   x  Kb 
3 3

 K eq   0.0788  x  0.01137 M
 0.0114  x  0.514  3x 
3
K f K sp
 0.0114  0.01137  M
%ppt'n=  100%  0.45%  0.1% . Thus, precipitation is not complete.
0.0114 M
4.
a.
Reaction ∆H°, kJ/mol ∆S°, J/(mol K)
CO( g )  H2 O( g ) CO2( g )  H2( g ) -41 -74.1
CH4( g )  H2 O( g ) CO( g )  3H2( g ) (-206)×-1 (-230.7) ×-1
2CO2( g )  6H2( g ) 2CH3 OH( g )  2H2 O( g ) (-49.1)×2 (-161.2) ×2
2CH3 OH( g ) CH3 OCH3( g )  H2 O( g ) (37)×-1 (23.8)×-1
CH4( g )  CO2( g )  2H2( g ) CH3 OCH3( g )  H2 O( g ) 29.8 -189.6

kJ 1000 J 189.6 J J
Go  Ho  TSo  29.8    298.15 K   8.633  104
mol 1 kJ mol K mol
J
8.633  104
Go  RT ln K p  mol  ln K p  K p  7.50  10 16
J
8.314  298.15 K
mol K
2

K p  K c (RT)n , n  (1  1)  (1  1  2)  2  K c  K p (RT)2  7.50  10 16   298.15 K  0.08206 mol

L atm 
K


K c  4.49×10-13
J
29800
K p2 Ho  1 1  K p, 3500 K mol  1  1  11
b. ln      ln 16
    K p, 3500 K  4.48  10
K p1 R  T2 T1  7.50  10 J  3500 K 298.15 K 
8.314
mol K
2
 L atm 
K c  K p (RT)2   4.48  10 11   3500 K  0.08206   3.69  10
6

 mol K 
CH4   CO2    H2   8.00 M  0.33  2.64 M, 4  H2 O  H2 O  8.00 M  0.01
 H2 O  0.016 M, CH3 OCH3   4  0.016 M=0.064 M
 H2 O CH3 OCH3   0.064  0.016 
Q   2.108  10 5  K c , therefore reaction will shift to reverse.
CH4  CO2  H2   2.64  2.64  2.64 
2 2

CH4 CO2 2H2 CH3OCH3 H2O

I 2.64 2.64 2.64 0.064 0.016
C +x +x +2x -x -x
E 2.64 + x 2.64 + x 2.64 + 2x 0.064 - x 0.016 - x

 0.064  x  0.016  x 
 3.695  10 6  x  0.01242 M
 2.64  x  2.64  x  2.64  2x 
2

CH4   CO2   2.64  x  2.652 M,  H2   2.64  2x  2.665 M

CH3 OCH3   0.064  x  0.05158 M,  H2 O  0.016  x  3.579×10-3 M
c. nCH4  nCO2  2.652 M  10.0 L  26.52 mol, n H2  2.665 M  10.0 L  26.65 mol
nCH3OCH3  0.05158 M  10.0 L  0.5158 mol, n H2O  3.579  103 M  10.0 L  0.03579 mol,
ntotal   2.652  2.652  2.665  0.05158  3.579  103   10.0 L  80.2484 mol
Find the moles of reactant added to the reaction vessel:
1 mol 1 mol 1 mol
5000 g CH4   311.72 mol, 8000 g CO2   181.78 mol, 1000 g H2   495.05 mol
16.04 g 44.01 g 2.02 g
1 mol
1000 g Ar   25.031 mol
39.95 g
Find the new moles of reactant:
nCH4  26.52 mol  311.72 mol  338.24 mol, nCO2  26.52 mol  181.78 mol  208.30 mol
n H2  26.65 mol  495.05 mol  521.70 mol
 Find the new total moles of the reaction vessel, and use Avogadro’s Law to find the final volume:
ntotal   338.24  208.30  521.70  0.5158  0.03579  25.031  1093.83 mol
n1 n 2  1093.83 mol 
  V2  10.0 L    136.31 L
V1 V2  80.2484 mol 
Find the new molarity of each reactant and product, and calculate Q:
338.24 mol 208.30 mol 521.70 mol
CH4    2.482 M, CO2    1.528 M,  H2    3.827 M
136.31 L 136.31 L 136.31 L
0.5158 mol 0.03579 mol
CH3 OCH3    3.784  103 M,  H2 O   2.626  10 4 M
136.31 L 136.31 L

Q
 3.784  10  2.626  10   1.788  10
3 4
8
 K c , thus the reaction will shift forward.
 2.482 1.528  3.827 
2

CH4 CO2 2H2 CH3OCH3 H2O

I 2.482 1.528 3.827 3.784×10-3 2.626×10-4
C -x -x -2x +x +x
E 2.482 - x 1.528 - x 3.827 - 2x 3.784×10-3 + x 2.626×10-4 + x

 3.784  10 3
 x  2.626  10 4  x 
 3.69  10 6  x  0.01223 M
 2.482  x 1.528  x  3.827  2x 
2

CH3 OCH3    3.784  103  0.01223 M  0.01601 M

L atm
Pfinal  0.01601 M  0.08206  3500 K  4.60 atm
mol K

5.
a. [Fe(CN)6]3- - red-orange, [Ni(CN)4]2- - yellow
0.01 M  10.00 mL M  mL cation
b. Mstd   0.001 M  Msample  std , Vtotal  20 mL
100 mL Vtotal
0.001 M  1.00 mL 0.001 M  4.00 mL
M1   5  105 M . M3   2  104 M .
20 mL 20 mL
0.001 M  2.00 mL 0.001 M  8.00 mL
M2   1 104 M M4   4  104 M
20 mL 20 mL

[Fe(CN)6]3- Absorbance [Ni(CN)4]2- Absorbance

5×10-5 0.5115 5×10-5 1.7810
1×10-4 1.0240 1×10-4 3.5610
2×10-4 2.0460 2×10-4 7.1200
4×10-4 4.0920 4×10-4 14.2400
[Fe(CN)6]3- - 10228.78x + 4.7826×10-4, [Ni(CN)4]2- - 35596.87x + 1.087×10-3.
slope 10228.78 M -1 35996.87 M -1
c.  , Fe complex   1022.88 M-1 cm-1 , Ni complex   3599.97 M-1 cm-1
path length 10 cm 10 cm
0.05 M  20 mL 0.01 M  mL Fe
d. For [Fe(CN)6]3-, M diluted CN   0.01 M, M Fe  , Vtotal  20.00 mL
100 mL Vtotal
0.01 M  mL CN-
MCN  , Vtotal  20.00 mL
Vtotal
0.01 M  4.00 mL
Solution 1: MCN  M Fe   2  103 M
20.00 mL
0.01 M  6.00 mL
Solution 2: MCN  M Fe   3  103 M
20.00 mL
0.01 M  7.50 mL
Solution 3: MCN  M Fe   3.75  10 3 M
20.00 mL
 Absorbance   y  int 
complexeq 
slope
3.40994  4.7826  10 4
Solution 1: complex eq   3.333  10 4 M
10228.78 M -1
5.11474  4.7826  10 4
Solution 2: complex eq   4.9999  104 M
10228.78 M -1
6.39334  4.7826  10 4
Solution 3: complex eq   6.2499  104 M
10228.78 M -1

3
Reaction: Fe(3aq )  6CN(aq ) Fe  CN 6 
( aq )

Fe3+ 6CN- [Fe(CN)6]3-

I MFe MCN 0
C -x -6x +x
E MFe – x MCN – 6x x

complexeq
Kf 
M  M 
6
CN  6 complex eq Fe  complex eq
3.333  10 4 M
Solution 1: K f   9.088  1041
 2  10 M   2  10 M
3 4 6 3 4
M  6  3.333  10 M  3.333  10
4.9999  10 4 M
Solution 2: K f   1.038  1042
 3  10 M   3  10 M
3 4 6 3 4
M  6  4.9999  10 M  4.9999  10
6.2499  10 4 M
Solution 3: K f   1.149  1042
 3.75  10 M   3.75  10 M
3 4 6 3 4
M  6  6.2499  10 M  6.2499  10
9.088  1041  1.038  1042  1.149  10 42
Average   1.032 ×1042
3

0.01 M  10 mL 0.001 M  mL Ni
For [Ni(CN)4]2-: M diluted CN   0.001 M, M Ni  , Vtotal  20.00 mL
100 mL Vtotal
0.001 M  mL CN-
MCN  , Vtotal  20.00 mL
Vtotal
0.001 M  4.00 mL
Solution 1: MCN  M Ni   2  104 M
20.00 mL
0.001 M  6.00 mL
Solution 2: MCN  M Ni   3  104 M
20.00 mL
0.001 M  7.50 mL
Solution 3: MCN  M Ni   3.75  10 4 M
20.00 mL

Absorbance   y  int 
complexeq 
slope
1.78083  1.087  10 3
Solution 1: complex eq   4.9997  10 5 M
35996.87 M -1
2.67075  1.087  10 3
Solution 2: complex eq   7.4997  10 5 M
35996.87 M -1
3.33819  1.087  10 3
Solution 3: complex eq  -1
 9.3747  10 5 M
35996.87 M
 2
Reaction: Ni (2aq )  4CN(aq )  Ni  CN 4 
( aq )

Ni2+ 4CN- [Ni(CN)4]2-

I MFe MCN 0
C -x -4x +x
E MNi – x MCN – 4x x

complexeq
Kf 
M  M 
4
CN  4  complex eq Ni  complex eq
4.9997  10 5 M
Solution 1: K f   2.055  1031
 2  104 M  4  4.9997  105 M   2  104 M  4.9997  105 M 
4

7.4997  10 5 M
Solution 2: K f   1.918  1031
 3  104 M  4  7.4997  105 M   3  104 M  7.4997  105 M 
4

9.3747  10 5 M
Solution 3: K f   1.823  1031
 3.75  104 M  4  9.3747  105 M   3.75  104 M  9.3747  105 M 
4

2.055  1031  1.918  1031  1.823  10 31

Average   1.932×1031
3

e. Note that the equation is not balanced. We can express the equilibrium of the equation in terms of the experimental K f values:
3
2Fe(3aq )  12CN(aq ) 2 Fe  CN 6   Kf 1 
2
( aq )

2 1
3 Ni  CN 4  3Ni (2aq )  12CN(aq )
 Kf 2 
3
( aq )

3 Ni  CN 4 
2
 2Fe 3
2 Fe  CN 6 
3
 3Ni 2
K eq 
 Kf 1 
2


1.032  10 
42 2

 1.476×10-10
 Kf 2  1.932  10 
( aq ) ( aq ) 3
( aq ) ( aq ) 31 3

6.
1 mol OH 1 1 mol solid
a. 8.43 ml  0.200 M     0.04215 M
1 mol HNO3 20 mL 2 mol OH
b.
Ba(OH)2 ● 8H2O Ba2+ 2OH- 8H2O
I --- 0 0 ---
C --- +x +2x ---
E --- x 2x ---
Ksp   x  2x   4x3  4(0.04215)3  3.00×10-4
2

c. The effect of adding NaOH or Ba(NO3)2 is common-ion effect. For the fourth medium:
10 mL  0.1 M
[OH ]   0.01 M
10 mL  90 mL
Ba(OH)2 ● 8H2O Ba2+ 2OH- 8H2O
I --- 0 0.01 ---
C --- +x +2x ---
E --- x 0.01 + 2x ---
 x  0.01  2x   3.00×10-4  x  0.03888 M  [OH ]  0.01  2  0.03888 M   0.08777 M
2

1 mol HNO3 1 mL titrant

0.08777 M  20 mL  -
  8.78 mL
1 mol OH 0.200 mmol
 For the final medium:
25 mL  0.1 M
[Ba 2  ]   0.025 M
25 mL  75 mL
Ba(OH)2 ● 8H2O Ba2+ 2OH- 8H2O
I --- 0.25 0 ---
C --- 0.25 +2x ---
E --- 0.25 + x 2x ---
 0.25  x  2x   3.00×10-4  x  0.03525 M  [OH ]  2  0.03525 M   0.07051 M
2

1 mol HNO3 1 mL titrant

0.07051 M  20 mL  -
  7.05 mL
1 mol OH 0.200 mmol
1 mol OH 1 1 mol solid
 0.0543 M  K sp  4  0.0543 M   6.404  10 4
3
d. 10.86 ml  0.200 M   
1 mol HNO3 20 mL 2 mol OH
1 mol OH 1 1 mol solid
 0.0771 M  K sp  4  0.0543 M   1.833  10 4
3
15.42 ml  0.200 M   
1 mol HNO3 20 mL 2 mol OH
H  1  S
Note that G  RT ln K  H  TS  ln K    . The equation is in linear form. By plotting lnK vs. 1/T we
R T R
can get the value of ∆H and ∆S.
1/T, K-1 lnK
3.354×10-3 -8.113
3.245×10-3 -7.353
3.095×10-3 -6.302
8.394 J 1 kJ kJ
Equation:-6981x + 15.3036, H  slope  R  6981 K    58.05
mol K 1000 J mol
8.394 J J
S  y  int R  15.036 K    127.23
mol K mol K
Note that the calculated ∆H and ∆S corresponds to the dissolution of Ba(OH)2 ● 8H2O (reverse of precipitation). Thus, the
kJ J
calculated ∆H and ∆S will change signs. Hprecipitation  -58.05 , Sprecipitation  -127.23
mol mol K

e. KCl, NaCl, NaNO3