CHAPTER 1: SUPPLEMENTARY PROBLEMS SP 1

MEASUREMENTS

S1-1. Write the following quantities in exponential notation, with one digit to the left of
the decimal point (e.g., 17 fC = 1.7 × 10-14 C):
(a) 2 TJ (c) 37 Mm (e) 842 pF
(b) 37 mm (d) 4 dK (f) 18.4 kPa

S1-2. Express the following quantities with abbreviations for units and prefixes from
Tables 1-1 through 1-3:
(a) 8 × 10-5 moles (c) 4 × 10-7 liters (e) 1.8 × 1014 hertz
(b) 1 × 1010 watts (d) 3 × 10-2 meters (f) 537 × 1010 ohms

S1-3. The lowest temperature attained in the laboratory in 1990 was 800 pK (for the
nuclei of silver atoms). Solid 3He has been cooled to 43 µK. Express the quotient
800 pK/43 µK in exponential notation (ie a × 10b).

S1-4. Use Table 1-4 to confirm that there are 760 torr in 1 atm.

S1-5. If 0.250 L of aqueous solution with a density of 1.00 g/mL contins 13.7 µg of
pesticide, express the concentration of pesticide in (a) ppm and (b) ppb.

S1-6. High purity water required in the semiconductor industry is purified by a process
called deionization in which most cations and anions are replaced by H+ and OH-,
respectively. (The product of H+ + OH- is just H2O.) The average concentrations
of some residual cations and anions left after deionization in one high purity
industrial water line are shown below:
Na+ 154 ng/L Cl- 172 ng/L
NH +4 58 ng/L Br- <10 ng/L
K+ 63 ng/L NO-3 26 ng/L
Mg2+ 73 ng/L HPO24- <30 ng/L
Ca2+ 45 ng/L SO24- 128 ng/L
Find the molar concentrations of Na+ and Cl- in this water. Use a prefix from
Table 1-3 to express your answers.

S1-7. Find the molarity of pyridine (C5H5N) if 5.00 g is dissolved in butanol to give a
total volume of 457 mL.

S1-8. A 95.0 wt % solution of ethanol (CH3CH2OH, MW 46.07) in water has a density

of 0.804 g/mL.
(a) Find the mass of 1.00 L of this solution and the number of grams of ethanol
per liter.
 SP Chapter 2: Supplementary Problems

(b) What is the molar concentration of ethanol in this solution?

(c) Find the molality of ethanol in this solution, considering H2O to be the
solvent (even though H2O is really the solute in this case).

S1-9. (a) How many grams of the element nickel are contained in 10.0 g of a 10.2
wt % solution of nickel sulfate hexahydrate, NiSO4. 6H2O (FW 262.85)?
(b) The concentration of this solution is 0.412 M. Find the density.

S1-10. Describe how to prepare exactly 100 mL of 1.00 M HCl from 12.1 M HCl reagent.

S1-11. Describe how to prepare approximately 100 mL of 0.082 m NaClO4 (FW 122.44).

S1-12. A 40.0 wt % solution of CsCl (FW 168.37) has a density of 1.43 g/mL, while a
20.0 wt % solution has a density of 1.18 g/mL.
(a) Find the molarity of CsCl in each solution.
(b) Find the molality of CsCl in each solution.
(c) How many mL of each solution should be diluted to 500 mL to make 0.100 M
reagent? Why doesn't it take twice as much of the 20.0 wt % solution as the
40.0 wt % solution?

S1-13. How many grams and how many mL of 40.0 wt % urea solution (density = 1.111
g/mL) are required to react with 4.00 mmol of Fe3+ in the following reactions?
(H2N)2CO + 3H2O → CO2 + 2NH +4 + 2OH-
Urea
Fe3+ + 3OH- + (x-1)H 2O → FeOOH. xH2O(s)

CHAPTER 2: SUPPLEMENTARY PROBLEMS

TOOLS OF THE TRADE

S2-1. Find the true mass of benzene (C6H6, density = 0.88 g/mL) if the apparent mass in
air is 9.947 g. Assume that the air density is 0.001 2 g/mL and the balance weight
density is 8.0 g/mL.

S2-2. An aqueous solution prepared when the lab temperature was 19°C had a
concentration 0.027 64 M. What is the concentration of the same solution when
used outdoors in the summer at 35°C?

S2-3. Water from a 5-mL pipet was drained into a weighing bottle whose empty mass
was 9.974 g to give a new mass of 14.974 g at 26°C. Find the volume of the pipet
at 26°C and at 20°C.
 CHAPTER 3: SUPPLEMENTARY PROBLEMS SP 3
EXPERIMENTAL ERROR

S3-1. Indicate how many significant figures there are in:

(a) 0.305 0 (b) 0.003 050 (c) 1.003 × 104

S3-2. Round each number as indicated:

(a) 5.124 8 to 4 significant figures (d) 0.135 237 1 to 4 significant figures
(b) 5.124 4 to 4 significant figures (e) 1.525 to 3 significant figures
(c) 5.124 5 to 4 significant figures (f) 1.525 007 to 3 significant figures

S3-3. Write each answer with the correct number of digits:

(a) 3.021 + 8.99 = 12.011 (e) log (2.2 × 10-18) = ?
(b) 12.7 - 1.83 = 10.87 (f) antilog (-2.224) = ?
(c) 6.345 × 2.2 = 13.959 0 (g) 10-4.555 = ?
(d) 0.030 2 ÷ (2.114 3 × 10-3) = 14.283 69

S3-4. Using the correct number of significant figures, find the formula weight of C6H13B.

S3-5. Find the absolute and percent relative uncertainty and express each answer with a
reasonable number of significant figures.
(a) 3.4 (±0.2) + 2.6 (±0.1) = ? (c) [3.4 (±0.2) × 10-8] ÷ [2.6 (±0.1) × 103] = ?
(b) 3.4 (±0.2) ÷ 2.6 (±0.1) = ? (d) [3.4 (±0.2) - 2.6 (±0.1)] × 3.4 (±0.2) = ?

S3-6. Express the molecular weight (± uncertainty) of benzene, C6H6, with the correct
number of significant figures.

S3-7. (a) A solution is prepared by dissolving 0.222 2 (±0.000 2) g of KIO3

[FW 214.001 0 (±0.000 9)] in 50.00 (±0.05) mL. Find the molarity and its
uncertainty with an appropriate number of significant figures.
(b) Would the answer be affected significantly if the reagent were only 99.9% pure?

S3-8. Find the absolute and percent relative uncertainty and express each answer with a
reasonable number of significant figures.
(a) 3.4 (±0.2) = ? (c) 103.4 (±0.2) = ? (e) log [3.4 (±0.2)] = ?
2
(b) [3.4 (±0.2)] = ? (d) e 3.4 (±0.2) =? (f) ln [3.4 (±0.2)] = ?

S3-9. The value of Boltzmann's constant (k) listed on the inside front cover of the book is
calculated from the quotient R/N, where R is the gas constant and N is Avogadro's
number. If the uncertainty in R is 0.000 070 J/(mol. K) and the uncertainty in N is
0.000 003 6 × 1023/mol, find the uncertainty in k.
 SP 4 Chapter 4: Supplementary Problems

S3-10. Find the absolute and percent relative uncertainty in the volume 150 mL delivered
with 3 aliquots of 50 mL from a Class A transfer pipet.

S3-11. Find the uncertainty in the molecular weight of B10H14 and write the molecular
weight with the correct number of significant figures.

CHAPTER 4: SUPPLEMENTARY PROBLEMS

STATISTICS AND SPREADSHEETS

S4-1. Consider Rayleigh's data for the mass of gas from air in Table 4-3. Find the
(a) mean (b) standard deviation (c) variance

S4-2. Suppose that a Gaussian population of measurements has a mean of 1 000 and a
standard deviation of 50. What fraction of the population lies in the following
intervals: (a) >1 000 (b) 950-1 050 (c) 850-1 150
(d) <900 (e) 930-1 030 (f) 912-991

S4-3. Write the equation of the smooth Gaussian curve in Figure 4-1. (Since the curve
represents the results of 4 768 measurements, and each bar on the graph
corresponds to a 20-h interval, you must use a factor of 4 768 × 20 in the numerator
of Equation 4-3.) Use the equation to calculate the value of y when x = 1000 h and
see if your calculated value agrees with the value on the graph.

S4-4. Find the 95 and 99% confidence intervals for the mean mass of nitrogen from
chemical sources in Table 4-3.

S4-5. Two methods were used to measure the specific activity (units of enzyme activity
per milligram of protein) of an enzyme. One unit of enzyme activity is defined as
the amount of enzyme that catalyzes the formation of one micromole of product per
minute under specified conditions.
Enzyme activity (five replications)
Method 1: 139 147 160 158 135
Method 2: 148 159 156 164 159
Is the mean value of method 1 significantly different from the mean value of method
2 at the 95% confidence level?
 Chapter 4: Supplementary Problems SP 5

S4-6. It is known from many careful measurements that the concentration of magnesium
in a material is 0.137 wt %. Your new analytical procedure gives values of 0.129,
0.133, 0.136, 0.130, 0.128 and 0.131 wt %. Do your results differ from the
expected result at the 95% confidence level?

S4-7. The Ti content (wt %) of two different ore samples was measured several times by
the same method. Are the mean values significantly different at the 95% confidence
level?
Sample 1: 0.013 4 0.013 8 0.012 8 0.013 3 0.013 7
Sample 2: 0.013 5 0.014 2 0.013 7 0.014 1 0.014 3

S4-8. The calcium content of a person's urine was determined on two different days:
Day Average Ca (mg/L) Number of measurements
1 238 4
2 255 5
The analysis applied to many samples yields a standard deviation of 14 mg/L. Are
the two averages significantly different at the 95% confidence level?

S4-9. Using the Q test, decide whether the value 0.195 should be rejected from the set of
results 0.217, 0.224, 0.195, 0.221, 0.221, 0.223.

S4-10. (a) The table on the next page lists rainfall measured in Los Angeles. Enter this
data into a spreadsheet and compute the average and standard deviation.
(b) Prepare a barchart showing rainfall as a function of year from 1878 to 1996.
(c) Prepare a histogram (another barchart) from this data showing rainfall in 2-year
intervals in the format below. For example, the bar at x = 15 will show the number
of years in which the rainfall was in the range 14.00 to 15.99 inches. In your
judgement, does rainfall follow a Gaussian distribution?
Number of years

15

10

0
1 3 5 7 9 1113 15 17 1921 23 2527 29 3133 35 3739 41
Inches of rain
 SP 6 Chapter 4: Supplementary Problems

Data for problem S4-10.

Year Rainfall (inches) Year Rainfall (inches) Year Rainfall (inches)

1878 20.860 1918 17.490 1958 17.490
1879 17.410 1919 8.820 1959 6.230
1880 18.650 1920 11.180 1960 9.570
1881 5.530 1921 19.850 1961 5.830
1882 10.740 1922 15.270 1962 15.370
1883 14.140 1923 6.250 1963 12.310
1884 40.290 1924 8.110 1964 7.980
1885 10.530 1925 8.940 1965 26.810
1886 16.720 1926 18.560 1966 12.910
1887 16.020 1927 18.630 1967 23.660
1888 20.820 1928 8.690 1968 7.580
1889 33.260 1929 8.320 1969 26.320
1890 12.690 1930 13.020 1970 16.540
1891 12.840 1931 18.930 1971 9.260
1892 18.720 1932 10.720 1972 6.540
1893 21.960 1933 18.760 1973 17.450
1894 7.510 1934 14.670 1974 16.690
1895 12.550 1935 14.490 1975 10.700
1896 11.800 1936 18.240 1976 11.010
1897 14.280 1937 17.970 1977 14.970
1898 4.830 1938 27.160 1978 30.570
1899 8.690 1939 12.060 1979 17.000
1900 11.300 1940 20.260 1980 26.330
1901 11.960 1941 31.280 1981 10.920
1902 13.120 1942 7.400 1982 14.410
1903 14.770 1943 22.570 1983 34.040
1904 11.880 1944 17.450 1984 8.900
1905 19.190 1945 12.780 1985 8.920
1906 21.460 1946 16.220 1986 18.000
1907 15.300 1947 4.130 1987 9.110
1908 13.740 1948 7.590 1988 11.570
1909 23.920 1949 10.630 1989 4.560
1910 4.890 1950 7.380 1990 6.490
1911 17.850 1951 14.330 1991 15.070
1912 9.780 1952 24.950 1992 22.650
1913 17.170 1953 4.080 1993 23.440
1914 23.210 1954 13.690 1994 8.690
1915 16.670 1955 11.890 1995 24.060
1916 23.290 1956 13.620 1996 17.750
1917 8.450 1957 13.240
 CHAPTER 5: SUPPLEMENTARY PROBLEMS SP 7
CALIBRATION METHODS

S5-1. (a) Use the method of least squares to calculate the equation of the best straight line
going through the points (1,3), (3,2), and (5,0). Express your answer in the
form y = [m(±σm)]x + [b(±σb)], with a reasonable number of significant
figures.
(b) Use the method of Equation 5-14 to find the value of x (and its uncertainty)
corresponding to y = 1.00.
(c) Use Equation 5-15 to find the uncertainty in x for y = 1.00. This is the correct
method.

S5-2. The signal (peak area) measured for different standard concentrations of silver in
atomic absorption is given below:
Ag (µg/mL): 0 8.0 16.0 32.0
Peak area: 0.002 0.076 0.147 0.282
(a) Construct a calibration curve and find the slope and intercept .
(b) Find the concentration of an unknown that gives a peak area of 0.160 when the
blank peak area is 0.004. That is, the corrected absorbance is 0.156.

S5-3. Propagation of uncertainty with a calibration curve. Refer to the data in the
previous problem. Use Equation 5-14 to find the concentration (and its uncertainty)
of an unknown with a corrected peak area of 0.156 (±sy).

S5-4. Standard addition. An unknown sample of dopamine gave a current of 34.6 nA in

an electrochemical analysis. Then 2.00 mL of solution containing 0.015 6 M
dopamine was mixed with 90.0 mL of unknown, and the mixture was diluted to
100.0 mL in a volumetric flask. The signal from the new solution was 58.4 nA.
(a) Denoting the initial, unknown concentration as [dopamine]i, write an
expression for the final concentration, [dopamine]f, after dilution.
(b) In a similar manner, write the final concentration of added standard dopamine,
designated as [S]f.
(c) Find [dopamine]i in the unknown.

S5-5. Internal standard. A mixture containing 80.0 nM iodoacetone (designated A) and

64.0 nM p-dichlorobenzene (designated B) gave the relative detector response (peak
area of A)/(peak area of B) = 0.71 in a chromatography experiment. A solution
containing an unknown quantity of A plus 930 nM B gave a relative detector
response (peak area of A)/(peak area of B) = 1.21. Find the concentration of A in
the unknown.
8

SP 8 Chapter 5: Supplementary Problems

S5-6. Standard addition. The quantity of acetylene (HC≡CH) in a gas mixture was
measured by mass spectrometry, in which the signal for mass number 26 is
proportional to the volume percent of acetylene.
Gas Signal (mV)
Blank containing no acetylene 0.2
Unknown 10.8
Unknown + 0.072 vol % C2H2 17.1
Unknown + 0.121 vol % C2H2 20.2
Unknown + 0.200 vol % C2H2 30.0
Unknown + 0.364 vol % C2H2 44.6
(a) Subtract the blank value (0.2 mV) from each measured signal. Prepare a graph
to find the volume percent of acetylene in the unknown.
(b) Use the method of least squares to find the uncertainties in slope and intercept
of your graph and to estimate the uncertainty in the answer to part a.

S5-7. Derivation of standard addition graphical treatment. Figure 5-6 is a graph of IS+X
vs. [S]f. Rearrange Equation 5-16 to the form IS+X = m[S]f + b, where m is the
slope and b is the intercept. The straight line in Figure 5-6 crosses the x axis when
IS+X = 0. Use your equation to show that when IS+X = 0, [S] = -[X]f.

S5-8. The lowest temperature achieved for systems of nuclear spins are listed below:

Year (= x) Temperature (K) Log [Temperature] (= y)

1979 5 × 10-8 -7.3
1983 2 × 10-8 -7.7
1989 2 × 10-9 -8.7
1990 8 × 10-10 -9.1

(a) Make a graph of y (= log [temperature]) versus. x (= year) and find the
slope and intercept and their standard deviations.
(b) Use the slope and intercept to extrapolate the line to predict the temperature
expected in the year 2010. (Do not consider uncertainties.) Is there any
reason to consider this a valid prediction? (Extrapolation means to go
beyond the measured data. Interpolation means to go between measured
data.)
 CHAPTER 6: SUPPLEMENTARY PROBLEMS SP 9
CHEMICAL EQUILIBRIUM

S6-1. Write the expression for the equilibrium constant for each of the following
reactions. Write the pressure of a gaseous molecule, X, as PX.
(a) Cl2(g) + 2OH-(aq) Cl-(aq) + OCl-(aq) + H2O(l)
(b) Hg(l) + I2(g) HgI2(s)

S6-2. Suppose that the following reaction has come to equilibrium:

Br (l) + I (s) + 4Cl-(aq)
2 2 2Br-(aq) + 2ICl - (aq)2
-
If more I2(s) is added, will the concentration of ICl2 in the aqueous phase increase,
decrease, or remain unchanged?

S6-3. From the equations CuN3(s) Cu+ + N 3- K = 4.9 × 10-9

HN 3 H+ + N 3- K = 2.2 × 10-5
find the value of K for the reaction Cu+ + HN 3 CuN3(s) + H + . All species are
aqueous unless otherwise indicated.

S6-4. For the reaction H2O(l) H+ (aq) + OH-(aq), K = 1.0 × 10-14 at 25˚C. The con-
centrations in a system out of equilibrium are [H+ ] = 3.0 × 10-5 M and [OH-] = 2.0
× 10-7 M. Will the reaction proceed to the left or to the right to reach equilibrium?

S6-5. For the sum of two reactions, we know that K3 = K 1K2.

A+B C+D K1
D+E B+F K2
A+E C+F K3
Show that this implies that ∆G˚3 = ∆G˚1 + ∆G˚2

S6-6. Find ∆G˚ for the reactions

(a) Ca(OH)2(s) Ca2+ + 2OH- K = 6.5 × 10-5
(b) Mg(OH)2(s) Mg2+ + 2OH- K = 7.1 × 10-12

S6-7. For the reaction Mg2+ + Cu(s) Mg(s) + Cu2+ , K = 10-92 and
∆S˚ = +18 J/(K. mol).
(a) Under standard conditions, is ∆G˚ positive or negative? The term "standard"
conditions" means that reactants and products are in their standard states.
(b) Under standard conditions, is the reaction endothermic or exothermic?

S6-8. Use the solubility product to calculate the solubility of Ag2CrO4 (FW 331.73)
(→ 2Ag+ + CrO2- 4 ) in water expressed as (a) moles per liter, (b) g/100 mL and (c)
ppm Ag (≈ µg Ag+ /mL).
+
 SP 10 Chapter 6: Supplementary Problems

S6-9. The solubility product for CuCl is 1.9 × 10-7. The equilibrium constant for the
reaction Cu(s) + Cu2+ 2Cu+ is 9.6 × 10-7. Calculate the equilibrium constant
for the reaction Cu(s) + Cu2+ + 2Cl- 2CuCl(s)

S6-10. How many grams of PbI2 (FW 461.0) will dissolve in 0.500 L of (a) water and
(b) 0.063 4 M NaI?

S6-11. What concentration of Ca2+ must be added to 0.010 M oxalate (C2O2-

4 ) to
precipitate 99.0% of the oxalate?

S6-12. Is it possible to separate 99.90% of 0.020 M Mg2+ from 0.10 M Ca2+ without
precipitation of Ca(OH)2 by addition of NaOH?

S6-13. Using Equations 6-11 to 6-15, calculate the concentrations of Pb2+ , PbI+ ,
PbI2(aq), PbI3- and PbI4- in a solution whose total I- concentration is somehow fixed
at 0.050 M. Compare your answers to Figure 6-2.

S6-14. Consider the following equilibria:

AgCl(s) Ag+ + Cl- Ksp = 1.8 × 10-10
AgCl(s) + Cl- AgCl2- K2 = 1.5 × 10-2
AgCl2- + Cl- AgCl2-
3 K3 = 0.49
Find the total concentration of silver-containing species in a silver-saturated,
aqueous solution containing the following concentrations of Cl-:
(a) 0.010 M (b) 0.20 M (c) 2.0 M

S6-15. Identify the Brønsted-Lowry acids on both sides of the reaction

NaHSO3 + NaOH Na2SO3 + H 2O

S6-16. Identify the conjugate acid-base pairs in the reaction

+
H2NCH 2CH2NH 2 + H 2O H3NCH2CH2NH 2 + OH-
Ethylenediamine

S6-17. Calculate the concentration of H+ and the pH of:

(a) 0.001 0 M HClO4 (d) 3.0 M NaOH
(b) 0.050 M HBr (e) 0.005 0 M [(CH3CH2)4N+ ]OH-
(c) 0.050 M LiOH tetraethylammonium hydroxide

S6-18. Write the Ka reaction for formic acid, HCO2H, and for methylammonium ion,
CH3NH 3+ .
 Chapter 6: Supplementary Problems SP 11

S6-19. Write the Kb reactions for piperidine and benzoate.

-
NH CO2

Piperidine Benzoate

S6-20. Write the Ka and Kb reactions of K2HPO4.

S6-21. Write the stepwise acid-base reactions for the following species in water. Write the
correct symbol (e.g., Kb1) for the equilibrium constant for each reaction.
-
CO2

-
HN NH CO2

Piperazine Phthalate ion

S6-22. Use Appendix G to decide which is the stronger acid: 3-nitrophenol or

4-nitrophenol. Write the acid dissociation reaction of each.

S6-23. Which is the stronger base: cyclohexylamine or imidazole? Write the base
hydrolysis reaction of each. In the case of imidazole, the nitrogen atom without a
hydrogen is the one that accepts H+ .
N
NH2
N
H

Cyclohexylamine Imidazole
pKB = 3.36 pKB = 7.01

S6-24. Write the Kb reaction of hypochlorite, OCl-. Given that the Ka value for HOCl is
3.0 × 10-8, calculate Kb for OCl-.

S6-25. Write the Ka2 reaction of H2SO4 and the Kb2 reaction the trisodium salt below.
ONa

NaO

ONa

S6-26. From the Ka values for citric acid in Appendix G, find Kb1, K b2 and Kb3 for
trisodium citrate.
 SP 12 CHAPTER 7: SUPPLEMENTARY PROBLEMS
LET THE TITRATIONS BEGIN

S7-1. How many milligrams of oxalic acid dihydrate, H2C2O4 . 2H2O (FW 126.07),
will react with 1.00 mL of 0.027 3 M ceric sulfate (Ce(SO4)2) if the reaction is
H2C2O4 + 2Ce4+ → 2CO2 + 2Ce3+ + 2H + ?

S7-2. A mixture weighing 27.73 mg containing only FeCl2 (FW 126.75) and KCl
(FW 74.55) required 18.49 mL of 0.022 37 M AgNO3 for complete titration of the
chloride. Find the mass of FeCl2 and the weight percent of Fe in the mixture.

S7-3. The chloride content of blood serum, cerebrospinal fluid or urine can be measured
by titration of the chloride with mercuric ion: Hg2+ + 2Cl- → HgCl2(aq). When
the reaction is complete, excess Hg2+ reacts with the indicator, diphenylcarbazone,
which forms a violet-blue color.
(a) Mercuric nitrate was standardized by titrating a solution containing 147.6 mg of
NaCl, which required 28.06 mL of Hg(NO3)2 solution. Find the molarity of
the Hg(NO3)2.
(b) When this same Hg(NO3)2 solution was used to titrate 2.000 mL of urine,
22.83 mL was required. Find the concentration of Cl- (mg/mL) in the urine.

S7-4. Consider the titration of 20.00 mL of 0.053 20 M KBr with 0.051 10 M AgNO3.
Calculate pAg+ at the following volumes of added AgNO3:
(a) 20.00 mL (b) Ve (c) 22.60 mL

S7-5. Consider the titration of 50.00 mL of 0.024 6 M Hg(NO3)2 with 0.104 M KSCN.
Calculate the value of pHg2+ at each of the following points and sketch the titration
curve: 0.25Ve, 0.5Ve, 0.75Ve, Ve, 1.05Ve, 1.25Ve.

S7-6. Calculate the value of pSO2-

4 at each of the following points in the titration of 100.0
mL of 0.050 0 M Sr2+ plus 0.050 0 M Ra2+ with 0.250 M SO2- 4 . Sketch the
titration curve. (a) 10.00 mL (d) 30.00 mL
(b) 19.00 mL (e) 40.00 mL
(c) 21.00 mL (f) 50.00 mL
 CHAPTER 8: SUPPLEMENTARY PROBLEMS SP 13
ACTIVITY

S8-1. Find the activity coefficient of each ion at the indicated ionic strength.:
(a) S2- (µ = 0.001 M) (c) Sn4+ (µ = 0.05 M)
3- -
(b) PO 4 (µ = 0.001 M) (d) H2NCH 2CO2 (µ = 0.01 M)

S8-2. Use interpolation in Table 8-1 to find the activity coefficient of OH- when µ =
0.030 M.

S8-3. Calculate the activity coefficient of formate, HCO2-, when µ = 0.038 M by using
(a) the extended Debye-Hückel equation (b) linear interpolation with Table 8-1

S8-4. Calculate the solubility of Ag2CrO4 (expressed as moles of CrO2-

4 per liter) in
(a) 0.050 M KClO4 (b) 0.005 0 M AgNO3

S8-5. Calculate the concentration of Tl+ in a saturated solution of TlBr in water.

S8-6. Find the pH of (a) 0.050 M HClO4 and (b) 0.050 M HClO4 plus 0.050 M HBr.
 SP 14 CHAPTER 9: SUPPLEMENTARY PROBLEMS
SYSTEMATIC TREATMENT OF EQUILIBRIUM

S9-1. Write a charge balance for an aqueous solution of glycine, which reacts as follows:
+ H 3NCH 2CO - H2NCH 2CO2- + H +
2
glycine
+ H 3NCH 2CO - + H 2O + H 3NCH 2CO2H + OH-
2

S9-2. Write a charge balance for a solution of Al(OH)3 dissolved in 1 M KOH. Possible
species are Al3+ , AlOH2+ , Al(OH)+2 , Al(OH)3 and Al(OH)4-.

S9-3. Write a mass balance for a 0.05 M solution of glycine (Problem S1) in water.

S9-4. Suppose that 0.30 g of AlOOH (FW 59.99) plus 150 mL of 3.0 M KOH are diluted
to l.00 L to give the same species produced by Al(OH)3 in Problem S9-2. Write
mass balance equations for aluminum and potassium.

S9-5. Use the systematic treatment of equilibrium to calculate the concentration of Hg2+
2 in
a saturated aqueous solution of (Hg2)3[Co(CN)6]2 which dissociates into
mercurous ion and Co(CN)3- 6 (cobalticyanide).

S9-6. A solution is prepared by mixing Mt moles of the salt MCl2 (which dissociates
completely to M2+ + 2Cl-) and Lt moles of the ligand HL in 1 L. The following
reactions may occur:
M2+ + L- ML+ K = 1.0 × 108 HL(aq) L- + H + Ka = 1.0 × 10-5
(a) Write a mass balance for the metal species.
(b) Write a mass balance for the ligand species.
(c) Write a charge balance.
(d) Suppose that Mt = Lt = 0.1 M (exactly) and the pH is somehow fixed at 5.00.
(This means that the charge balance no longer applies.) Use the equilibria and
the two mass balances to find the concentrations of ML+ , M2+ , L -, and HL.

S9-7. (a) Use the procedure in Section 9-4 to find the concentrations of Mg2+ , F -, and
HF in a saturated aqueous solution of MgF2 held at pH 3.00.
(b) Look up the formation constant for MgF+ in the Appendix. Using the
concentrations of Mg2+ and F- from (a), calculate the concentration of MgF+ .
Is it negligible compared to [Mg2+ ]? (The answer is no.)
(c) Because [MgF+ ] is not negligible compared to [Mg2+ ], we need to alter the
mass balance to solve this problem correctly. Write the mass balance including
the species MgF+ .
 15

Chapter 9: Supplementary Problems SP 15

S9-8. The acid HA has a solubility of 0.008 5 M in water at 25°C.

Ks
HA(s) HA(aq) Ks = [HA(aq] = 0.008 5 (a)
If NaOH is added to a suspension of solid HA in water, more acid dissolves
because of the reaction
K = 6.3×105
HA(aq) + OH- A-(aq) + H2O (b)
Consider a saturated solution, whose pH is somehow fixed at 10.00, in contact
with excess solid HA. Calculate the total concentration of HA + A-.

S9-9. Consider a saturated solution of SrSO4 in which the following reactions can occur:
SrSO4(s) Sr2+ + SO2-4 Ksp = 3.2 × 10-7
SO2-
4 + H 2O HSO4- + OH- Kb = 9.8 × 10-13
(a) Write mass and charge balances for this solution.
(b) Find the concentration of Sr2+ in the solution if the pH is fixed at 2.50.

S9-10. The previous problem neglected ion pair formation:

Sr2+ + SO2-4 SrSO4(aq) K = 1.6 × 102
(a) Write the mass balance including the ion pair.
(b) Find the concentrations of Sr2+ and SrSO4(aq) if the pH is fixed at 2.50. What
fraction of dissolved strontium is in the ion pair?

S9-11. Consider a saturated solution of calcium oxalate, CaC2O4, in which the following
reactions can occur:
CaC2O4(s) Ca2+ + C2O2-
4 Ksp = 1.3 × 10-8
2- -
C2O4 + H 2O HC2O4 + OH- Kb1 = 1.8 × 10-10
HC2O4- + H 2O H2C2O4 + OH- Kb2 = 1.8 × 10-13
(a) Write mass and charge balances for this solution.
(b) Find the concentration of Ca2+ in the solution if the pH is fixed at 2.30.

S9-12. Consider a saturated solution of zinc arsenate, Zn3(AsO4)2, in which the following
reactions can occur: Zn3(AsO4)2(s) 3Zn2+ + 2AsO3- 4 Ksp = 1.0 × 10-27
3- 2-
AsO 4 + H 2O HAsO4 + OH- Kb1 = 3.1 × 10-3
HAsO2-4 + H 2O H2AsO4- + OH- Kb2 = 9.1 × 10-8
-
H2AsO4 + H 2O H3AsO4 + OH- Kb3 = 1.7 × 10-12
(a) Write mass and charge balances for this solution.
(b) Find the concentration of Zn2+ in the solution if the pH is fixed at 6.00.

S9-13. Use the data in Problem S9-6 to construct a graph showing the concentrations of
M2+ , ML+ , L - and HL as a function of pH from 0 to 14 in 0.5 increments.
 SP 16 CHAPTER 10: SUPPLEMENTARY PROBLEMS
MONOPROTIC ACID-BASE EQUILIBRIA

S10-1. Calculate the pH of (a) 5.0 × 10-4 M HNO3 and (b) 5.0 × 10-4 M (CH3)4N+ OH-.

S10-2. Calculate the pH of 2.0 × 10-7 M (CH3)4N+ OH-. What fraction of the total OH- in
this solution is derived from dissociation of water?

S10-3. Using activity coefficients correctly, calculate the pH of

(a) 0.050 M HBr (b) 0.050 M NaOH

S10-4. Using Appendix G, write structures of pyridine and pyridinium nitrate

(pyridine. HNO3). Write the Kb reaction for pyridine and find the values of Kb and
pKb.

S10-5. Find the pH and fraction of dissociation (α) of a 0.010 0 M solution of the weak
acid HA with Ka = 1.00 × 10-4.

S10-6. Calculate the pH of 0.085 0 M pyridinium bromide, C5H5NH + Br-.

S10-7. Find the pH and concentrations of cyclohexylamine (C6H11NH 2) and cyclohexyl-

ammonium ion (C6H11NH +3 ) in a 0.020 M solution of cyclohexylammonium
iodide.

S10-8. A 0.100 M solution of the weak acid HA has a pH of 2.36. Calculate pKa for HA.

S10-9. (a) Calculate the pH and fraction of dissociation of 10-2.00 M hexane-2,4-dione.

(b) Calculate the pH and fraction of dissociation of 10-9.00 M hexane-2,4-dione.

S10-10. Compound A reacts with H2O as follows:

O O-
C6 H5 O C6 H5 O
+ H2O = H + H+
H O O
HO
O O

The equilibrium constant (in aqueous methanol solution) is 10-5.4. Suppose that
this same equilibrium constant applies in pure water. Find the pH of a 0.020 M
solution of compound A.

S10-11. Find the pH and fraction of association (α) of a 0.050 M solution of the weak base
B with Kb = 1.00 × 10-4.

S10-12. Find the pH and concentrations of (CH3CH2)2NH and (CH 3CH2)2NH +2 in a

 Chapter 10: Supplementary Problems SP 17

0.030 M solution of diethylamine.

S10-13. Find the pH and fraction of association (α) of 0.026 M NaOCl.

S10-14. Calculate the fraction of association (α) for 1.00 × 10-1, 1.00 × 10-2, and
1.00 × 10-12 M sodium formate.

S10-15. If a 0.030 M solution of a base has pH = 10.50, find Kb for the base.

S10-16. If a 0.030 M solution of a base is 0.27% hydrolyzed (α = 0.002 7), find Kb for the
base.

S10-17. Calculate the pH and fraction of association of 10-2.00 M sodium hexane-2,4-

dionate. (This salt is derived from the acid hexane-2,4-dione in Appendix G.)

sodium hexane-2,4-dionate

S10-18. Which buffer system will have the greatest buffer capacity at pH 8.5?
(a) dimethylamine / dimethylammonium ion
(b) ammonia / ammonium ion
(c) hydroxylamine / hydroxylammonium ion
(d) 3-nitrophenol / 3-nitrophenolate ion

S10-19. Find the pH of a solution prepared from 2.53 g of oxoacetic acid, 5.13 g of
potassium oxoacetate and 103 g of water.
O CO2H O CO2- K +

H H
Oxoacetic acid Potassium oxoacetate
MW 74.036 MW 112.126

S10-20. Write the Henderson-Hasselbalch equation for a solution of methylamine.

Calculate the quotient [CH3NH 2]/[CH3NH +3 ] at (a) pH 4.00, (b) pH 10.64 and (c)
pH 12.00.

S10-21. Given that pKb for iodate ion IO3- is 13.83, find the quotient [HIO3 ]/[IO3-] in a
solution of sodium iodate at (a) pH 7.00 and (b) pH 1.00.

S10-22. (a) Calculate the pH of a solution prepared by dissolving 10.0 g of

 SP 18 Chapter 10: Supplementary Problems

tris(hydroxymethyl)aminomethane ("tris") plus 10.0 g of tris hydrochloride in

0.250 L of water.
(b) What will be the pH if 10.5 mL of 0.500 M NaOH is added?

S10-23. How many milliliters of 0.113 M HBr should be added to 52.2 mL of 0.013 4 M
morpholine to give a pH of 8.00?

S10-24. (a) Calculate how many milliliters of 0.100 M HCl should be added to how many
grams of sodium acetate dihydrate (NaOAc . 2H2O, FW 118.06) at 5˚C to
prepare 250.0 mL of 0.100 M buffer, pH 5.00. At 5˚C, pKw = 14.734 and
pKa for acetic acid is 4.770.
(b) If you mixed what you calculated in part a, the pH would not be 5.00.
Describe how you would actually prepare this buffer in the lab.

S10-25. Use Equations 10-20 and 10-21 to find the concentrations of B and BH+ in a
solution prepared by mixing 0.000 100 mol of propylamine plus 0.000 100 mol of
propylammonium chloride in 1.00 L of water.

S10-26. (a) Use the systematic treatment of equilibrium (neglecting activity coefficients) to
write all of the equations necessary to find [OH-] in a solution of a weak base,
B, whose equilibrium constant is Kb and whose formal concentration is F.
Combine the equations so that the only variable is [OH-] and rearrange your
answer to the form [OH-]3 + a[OH-]2 + b[OH-] + c = 0.
(b) Use a spreadsheet to find the pH of 10-3 M B with Kb = 10-5 and of 10-5 M B
with Kb = 10-9. You can solve the cubic polynomial by guessing values of
[OH-] and having the spreadsheet evaluate the polynomial. When the
polynomial is zero, you have guessed the correct value of [OH-].
 CHAPTER 11: SUPPLEMENTARY PROBLEMS SP 19
POLYPROTIC ACID-BASE EQULIBRIA

S11-1. Write the chemical reactions whose equilibrium constants are Kb1 and Kb2 for the
amino acid serine. Find the values of Kb1 and Kb2.

S11-2. Consider the diprotic acid H2A with K1 = 1.00 × 10-5 and K2 = 1.00 × 10-9. Find
the pH and concentrations of H2A, HA- , and A2- in the following solutions: (a)
0.100 M H 2A, (b) 0.100 M NaHA, and (c) 0.100 M Na2A.

S11-3. Find the pH of 0.150 M piperazine monohydrochloride, piperazine . HCl.

Calculate the concentration of each form of piperazine in this solution.

S11-4. Write down, but do not attempt to solve, the exact equations needed to calculate the
composition of one liter of solution containing F 1 mol of HCl, F 2 mol of disodium
ascorbate (Na2A, the salt of a weak acid whose two Ka values may be called K1
and K2), and F 3 mol of trimethylamine (a weak base, B, whose equilibrium
constant should be called Kb). Include activity coefficients wherever appropriate.

S11-5. How many mL of 0.423 M KOH should be added to 5.00 g of tartaric acid
(2,3-dihydroxybutanedioic acid, FW 150.08) before diluting to 50 mL to give a
buffer of (a) pH 3.00 and (b) pH 4.00?

S11-6. How many mL of 0.421 M HCl should be added to 50.0 mL of 0.055 5 M

disodium malonate (NaO2CCH2CO2Na, FW 148.03, the salt of malonic acid) to
adjust the pH to (a) 6.00 and (b) 3.20?

S11-7. How many grams of oxalic acid (FW 90.04) should be mixed with 5.00 g of
K2C2O4 (FW 166.22) to give a pH of 3.20 when diluted to 250 mL?

S11-8. Starting with the fully protonated species, write the stepwise acid dissociation
reactions of the amino acids aspartic acid and arginine. Be sure to remove the
protons in the correct order. Which species are the neutral molecules that we call
aspartic acid and arginine?

S11-9. (a) Find the quotient [H2His+ ]/[HHis] in a 0.050 0 M histidine solution.
(b) Find the same quotient for 0.050 0 M histidine monohydrochloride (His . HCl).

S11-10. Find the pH and concentration of each species of arginine in 0.012 0 M

arginine. HCl solution.

S11-11. Consider the neutral base pyrrolidine, C4H9N, designated B.

(a) Which is the predominant species, B or BH+ , at pH 11? at pH 12?
 SP 20 Chapter 11: Supplementary Problems

(b) At what pH is [BH+ ] = [B]?

(c) What is the quotient [B]/[BH+ ] at pH 12.00? at pH 2.00?
S11-12. Which is the predominant form of sulfurous acid at pH (a) 2, (b) 4, (c) 6 and (d) 8?

S11-13. What is the charge of the predominant form of citric acid at pH 5.00?

S11-14. The acid HA has pKa = 7.00. Use Equations 11-17 and 11-18 to find the fraction
in the form HA and the fraction in the form A- at pH = 8.00. Does your answer
agree with what you expect for the quotient [A-]/[HA] at pH 8.00?

S11-15. A dibasic compound, B, has pKb1 = 2.00 and pKb2 = 8.00. Find the fraction in
the form BH22+ at pH 9.00 using Equation 11-19. Note that K1 and K2 in Equation
11-19 are acid dissociation constants for BH22+ (K1 = K w/Kb2 and K2 = K w/Kb1).

S11-16. What fraction of 1,6-hexanedoic acid (adipic acid) is in each form (H2A, HA-, A2-)
at pH 5.00? at pH 6.00?

S11-17. Calculate α H2A, α HA-, and α A2- for butane-2,3-dione dioxime (dimethylglyoxime)
at pH 10.00, 10.66, 11.00, 12.00, and 12.50.

S11-18. Calculate the isoelectric and isoionic pH of 0.010 M 8-hydroxyquinoline.

 CHAPTER 12: SUPPLEMENTARY PROBLEMS SP 21
ACID-BASE TITRATIONS

S12-1. Consider the titration of 25.0 mL of 0.050 0 M HClO4 with 0.100 M KOH. Find
the pH at the following volumes of base added and make a graph of pH versus Vb:
Vb = 0, 1, 5, 10, 12.4, 12.5, 12.6 and 13 mL.

S12-2. A volume of 50.0 mL of 0.050 0 M weak acid HA (pKa = 4.00) was titrated with
0.500 M [CH 3]4N+ OH- (tetramethylammonium hydroxide, a strong base). Find
the pH at the following volumes of base added and make a graph of pH versus Vb:
Vb = 0, 1, 2.5, 4, 4.9, 5, 5.1, and 6 mL.

S12-3. Using the same instructions as Problem 12-7, sketch the titration curve for the
reaction of 50.0 mL of 0.050 0 M 4-nitrophenol with 0.100 M NaOH.

S12-4. When 16.24 mL of 0.064 3 M KOH was added to 25.00 mL of 0.093 8 M weak
acid, HA, the observed pH was 3.62. Find pKa for the acid.

S12-5. A 50.0-mL aliquot of 0.050 M weak base B (pKb = 4.00) was titrated with
0.500 M HNO3. Find the pH at the following volumes of acid added and make a
graph of pH versus Va: Va = 0, 1, 2.5, 4, 4.9, 5, 5.1, and 6 mL.

S12-6. A solution of 100.00 mL of 0.040 0 M sodium propanoate (the sodium salt of

propanoic acid) was titrated with 0.083 7 M HCl. Calculate the pH at the points Va
= 0, 14Ve, 12Ve, 34Ve, Ve, and 1.1 Ve.

S12-7. A volume of 50.0 mL of the dibasic compound B (0.050 0 M, pKb1 = 5.00, pKb2
= 9.00) was titrated with 0.500 M HCl. Find the pH at the following volumes of
acid added and make a graph of pH versus Va: Va = 0, 1, 2.5, 4, 4.8, 5, 5.2, 6,
7.5, 9, 9.8,10, 10.2, 11 and 12 mL.

S12-8. A 50.0-mL aliquot of 0.050 0 M diprotic acid H2A (pK1 = 5.00, pK2 = 9.00) was
titrated with 0.500 M NaOH. Find the pH at the following volumes of base added
and make a graph of pH versus Vb: Vb = 0, 1, 2.5, 4, 4.8, 5, 5.2, 6, 7.5, 9,
9.8,10, 10.2, 11 and 12 mL.

S12-9. Calculate the pH at 2-mL intervals (from 0 to 12 mL) in the titration of 25.0 mL of
0.100 M cyclohexylamine with 0.250 M HI. Make a graph of pH versus Va.

S12-10. A solution containing 0.010 0 M tyrosine was titrated to the first equivalence point
with 0.004 00 M KOH.
(a) Draw the structures of reactants and products.
 SP 22 Chapter 12: Supplementary Problems

(b) Calculate the pH at the first equivalence point.

S12-11. How many milliliters of 0.043 1 M NaOH should be added to 59.6 mL of 0.122 M
leucine to obtain a pH of 8.00?

S12-12. Consider the neutral form of the amino acid histidine, which we will abbreviate HA.
(a) Write the sequence of reactions that occurs when HA is titrated with HClO4.
Draw structures of reactants and products.
(b) How many mL of 0.050 0 M HClO4 should be added to 25.0 mL of 0.040 0 M
HA to give a pH of 3.00?

S12-13. What color change would you expect to see during the upper titration in Figure 12-4
with bromothymol blue indicator?

S12-14. Cresol purple has two transition ranges listed in Table 12-4. What color would
you expect it to be at the following pH values?
(a) 1 (b) 3 (c) 7 (d) 10

S12-15. Why would an indicator end point not be very useful in the titration curve for
pKa = 10.00 in Figure 12-3?

S12-16. Consider the titration of 0.10 M pyridinium bromide (the salt of pyridine plus HBr)
by 0.10 M NaOH. Sketch the titration curve using calculated pH values for the
volumes 0.99 Ve, Ve, and 1.01 Ve. Select an indicator from Table 12-4 that would
be suitable for this titration and state what color change will be used.

S12-17. A very weak basic aromatic amine (pKb = 14.79) was used to measure the pH of a
concentrated acid. A solution was prepared by dissolving 6.390 mg of the amine
(MW 278.16) in 100.0 mL of the acid. The absorbance measured at 385 nm in a
1.000-cm cell was 0.350. Find the pH of the solution
B + H+ BH+
ε385 = 2 860 M-1 cm-1 ε385 = 937 M-1 cm-1

S12-18. An aqueous solution containing ~1 g of oxobutanedioic acid (MW 132.073) per

100 mL was titrated with 0.094 32 M NaOH to measure the acid molarity.
(a) What will be the pH at each equivalence point?
(b) Which equivalence point would be best to use in this titration?
(c) You have the indicators erythrosine, ethyl orange, bromocresol green,
bromothymol blue, thymolphthalein, and alizarin yellow. Which indicator will
you use and what color change will you look for?
 Chapter 12: Supplementary Problems SP 23

S12-19. Borax (Table 12-5) was used to standardize a solution of HNO3. Titration of
0.261 9 g of borax required 21.61 mL. What is the molarity of the HNO3?

S12-20. Derive the equation in Table 12-6 for titrating dibasic B with strong acid.

S12-21. Activity coefficients in titration equations. In the titration of a weak acid by a strong
base, activity coefficients do not enter the charge or mass balances and therefore do
not appear in Equation 12-9. In a rigorous treatment, the only way activity
coefficients enter any of the equations in Table 12-6 is in the fractional composition
equations. Using activity coefficients correctly, derive the following expressions
for α HA and α A-. These are the expressions that should be used with Equation
12-9 in a rigorous treatment of a titration.
[H+ ]γH+ γA- KaγHA
α HA = α A- =
[H+ ]γH+ γA- + K aγHA [H+ ]γH+ γA- + K aγHA
 SP 24 CHAPTER 13: SUPPLEMENTARY PROBLEMS
EDTA TITRATIONS

S13-1. Calculate α Y4- for EDTA at pH 6.62.

S13-2. (a) Find the conditional formation constant for Ca(EDTA)2- at pH 10.00.
(b) Find the concentration of free Ca2+ in 0.050 M Na2[Ca(EDTA)] at pH 10.00.

S13-3. A brainbuster! What is the quotient [MgY2-]/[NaY3-] in a solution prepared by

mixing 0.100 M Na2EDTA with an equal volume of 0.100 M Mg(NO3)2? Assume
that the pH is high enough that there is a negligible amount of unbound EDTA.
You can approach this problem by realizing that nearly all Mg2+ will be bound to
EDTA and nearly all Na+ will be free.

S13-4. Consider the titration of 100.0 mL of 0.050 0 M EDTA at pH 10.00 with 0.100 M
metal ion, Mn+ .
(a) What is the equivalence volume, Ve, in milliliters?
(b) Calculate the concentration of total free EDTA at V = 12Ve.
(c) What fraction (α 4-) of free EDTA is in the form Y4- at pH 10.00?
Y
(d) The formation constant (Kf) is 108.00 . Calculate the value of the conditional
formation constant K'f (= α Y4- Kf).
(e) Calculate the concentration of free metal ion at V = Ve.
(f) What is the concentration of total free EDTA ion at V = 1.100 Ve?

S13-5. Calculate pFe2+ at each of the following points in the titration of 25.00 mL of
0.020 26 M EDTA by 0.038 55 M Fe2+ at pH 6.00:
(a) 12.00 mL (b) Ve (c) 14.00 mL

S13-6. Consider the titration of 50.0 mL of 0.011 1 M Y3+ (Y = yttrium) with 0.022 2 M
EDTA at pH 5.00. Calculate pY3+ at the following volumes of added EDTA and
sketch the titration curve:
(a) 0 mL (d) 24.0 mL (g) 25.1 mL
(b) 10.0 mL (e) 24.9 mL (h) 26.0 mL
(c) 20.0 mL (f) 25.0mL (i) 30.0 mL

S13-7. Calculate pCd2+ at each of the following points in the titration of 10.00 mL of
0.001 00 M Cd2+ with 0.002 00 M EDTA at pH 12.00 in a solution whose NH3
concentration is somehow fixed at 0.200 M:
(a) 0 mL (c) 4.90 mL (e) 5.10 mL
(b) 1.00 mL (d) 5.00 mL (f) 6.00 mL
 Chapter 13: Supplementary Problems SP 25

S13-8. Allosteric interactions. The molecule drawn below contains two large rings with
oxygen atoms capable of binding metal atoms, one on each ring.

O O
O O O O

O O O O
O O

Calling the molecule L, we can represent the metal-binding reactions as

[LM]
L + M LM K1 = [L][M] (A)

[LM2]
LM + M LM2 K2 [LM][M] (B)

If binding at one site influences binding at the other site, there is said to be an
allosteric interaction between the sites. If biding at one site makes binding at the
other site more favorable than it was in the absence of the first binding, there is said
to be positive cooperativity between the sites. If binding at one site makes biding at
the second site less favorable, there is negative cooperativity between the sites. If
there is no interaction between sites, binding is said to be noncooperative. This
means that a metal at one site has no effect on metal binding at the other site.
The binding of Hg(CF3)2 to the molecule above in benzene solution was found
to have K1 = 4.0 (±0.1) K2 [J. Rebek, Jr., T. Costello, L. Marshall, R. Wattley,
R. C. Gadwood, and K. Onan, J. Amer. Chem. Soc. 1985, 107, 7481]. Show
that K1 = 4K 2 corresponds to noncooperative binding.
Hint: If the two binding sites are represented as we can represent the
equilibria as follows:
K1 K2
= + =

where represents metal bound at one site. In noncooperative binding, the four
populations , , , and must be equal when the ligand
is 50% saturated with metal.

S13-9. EDTA at pH 5 was titrated with standard Pb2+ using xylenol orange as indicator
(Table 13-3). Which is the principal species of the indicator at pH 5? What color
was observed before the equivalence point? after the equivalence point? What
would be the color change if the titration were conducted at pH 8 instead of pH 5?
 SP 26 Chapter 13: Supplementary Problems

S13-10. A 25.00-mL sample containing Fe3+ was treated with 10.00 mL of 0.036 7 M
EDTA to complex all the Fe3+ and leave excess EDTA in solution. The excess
EDTA was then back-titrated, requiring 2.37 mL of 0.046 1 M Mg2+ . What was
the concentration of Fe3+ in the original solution?

S13-11. Express the hardness of water containing 3.2 mM Ca2+ + 1.1 mM Mg2+ in terms
of mg CaCO3/L. (FW CaCO3 100.09)

S13-12. Cyanide can be determined indirectly by EDTA titration. A known excess of Ni2+
is added to the cyanide to form tetracyanonickelate:
4CN- + Ni2+ → Ni(CN)2- 4

When the excess Ni2+ is titrated with standard EDTA, Ni(CN)24- does not react. In
a cyanide analysis 12.7 mL of cyanide solution was treated with 25.0 mL of
standard solution containing excess Ni2+ to form tetracyanonickelate. The excess
Ni2+ required 10.1 mL of 0.013 0 M EDTA for complete reaction. In a separate
experiment, 39.3 mL of 0.013 0 M EDTA was required to react with 30.0 mL of
the standard Ni2+ solution. Calculate the molarity of CN- in the 12.7-mL sample of
unknown.

S13-13. A mixture of Mn2+ , Mg2+ , and Zn2+ was analyzed as follows: The 25.00-mL
sample was treated with 0.25 g of NH3OH+ Cl- (hydroxylammonium chloride, a
reducing agent that maintains manganese in the +2 state), 10 mL of ammonia buffer
(pH 10), and a few drops of eriochrome black T indicator and then diluted to 100
mL. It was warmed to 40˚C and titrated with 39.98 mL of 0.045 00 M EDTA to
the blue end point. Then 2.5 g of NaF was added to displace Mg2+ from its EDTA
complex. The liberated EDTA required 10.26 mL of standard 0.020 65 M Mn2+
for complete titration. After this second end point was reached, 5 mL of 15 wt %
aqueous KCN was added to displace Zn2+ from its EDTA complex. This time the
liberated EDTA required 15.47 mL of standard 0.020 65 M Mn2+ . Calculate the
number of milligrams of each metal (Mn2+ , Zn 2+ , and Mg2+ ) in the 25.00-mL
sample of unknown.

S13-14. Here is a procedure for the consecutive determination of Bi3+ , Ti4+ and Al3+ in a
mixture that might arise in the analysis of aluminum ore, clays or cements
[M. A. El-Hamied Hafez, Talanta 1992, 39, 1189].
(1) The solution is acidified to pH 1-2 with HNO3, at which only Bi3+ has a large
enough conditional formation constant to be titrated. The indicator semixylenol
orange is added and the solution is titrated with standard EDTA until just
 Chapter 13: Supplementary Problems SP 27

reaching the end point color change from red (MIn) to yellow (In). This gives
the Bi3+ content of the solution and leaves Ti4+ and Al3+ uncomplexed.
(2) Then excess EDTA is added and the pH is raised to 5 with hexamine, which
serves as a buffer and an auxiliary complexing ligand.
N
Hexamine ((CH2)6N4)
N (also called hexamethylenetetramine)
N pK a for (CH2)6N4H+ = 5.1
N

The solution is boiled to complete the reaction with EDTA, cooled and titrated
with Zn2+ until just reaching the end point color change from yellow (In) to red
(MIn). Now the solution contains Bi(EDTA)-, Ti(EDTA) and Al(EDTA)-, with
no excess EDTA.
(3) Excess H2PO-4 is added and the solution is boiled to displace Ti4+ from
EDTA. Titration with standard Zn2+ until the end point color change is just
reached gives the Ti4+ content.
(4) Finally, excess F- is added and the solution is boiled to displace Al3+ from
EDTA. Titration of the hot solution with standard Zn2+ until the end point color
change is just reached gives the Al3+ content.

In step 1, 25.00 mL of unknown required 16.43 mL of 0.010 44 M EDTA. Step 3

required 4.22 mL of 0.012 76 M Zn2+ and step 4 consumed 25.92 mL of 0.012 76
M Zn2+ . Find the molarity of each cation in the original unknown. What color
change is observed in steps (3) and (4)?

S13-15. A Spectrophotometric Metal-Ligand Binding Problem Using

Nonlinear Least-Squares Curve Fitting
The spectrum on the next page shows changes that occur as metal M is titrated with
ligand L.
K [ML]
M + L ML K = [M][L]

Curve 0 is the spectrum of M and curves 1 through 5 result from additions of L.

The species M and ML absorb in the region shown, but L has no absorbance. Both
the initial solution and the titrant solution contain 2.12 × 10-4 M metal ion, so the
total concentration of M plus ML remains constant throughout the experiment:
 SP 28 Chapter 13: Supplementary Problems

0.8
1
2

3
Absorbance

0.6
4

0
5
0.4
5

0.2

0
0
500 550 600 650
Wavelength (nm)

Spectrophotometric titration of species P (curve 0) with ligand X (curves 1-5). [From

J. R. Long and R.S. Drago, J. Chem. Ed. 1982 , 59, 1037.]

Mass balance for M: Cm = [M] + [ML] = 2.12 × 10-4 M

Mass balance for L: Cl = [L] + [ML]
where Cl is the total ligand concentration after each addition. Substituting
[M] = Cm - [ML] and [L] = Cl - [ML] into the equilibrium constant above, you can
solve for [ML]:
1 1 2
 Cm + C l + 1  - 4C mCl 

[ML] = 2   Cm + C l + K -
   K 
Now we want to express the absorbance changes as a function of K and various
known quantities. For a 1-cm-pathlength cell, you can show from Beer's law that
the change of absorbance (∆A) at a given wavelength can be written
∆A = ∆ε[ML]
where ∆ε is the change in molar absorptivity between product and reactant∆ε
( =
εML - εM). Substituting in the expression for [ML] above gives

∆ε  1 2 
∆A = 2   Cm + C l + K -  Cm + C l + 1  - 4C mCl 
   K 

The least-squares problem: The table below gives∆A as a function of Cl.

Chapter 13: Supplementary Problems SP 29

Absorbance
Curve Cl (M) at 525 nm ∆A
0 0 0.859 ---
1 0.515 × 10-3 0.745 -0.114
2 1.03 × 10-3 0.676 -0.183
3 2.06 × 10-3 0.609 -0.250
4 4.11 × 10-3 0.544 -0.315
5 9.23 × 10-3 0.494 -0.365
Your job is to use a nonlinear least squares curve fitting procedure to find the best
values of ∆ε and K in the equation ∆A = f(Cl, ∆ε, K) where Cl is the
independent variable (x), ∆A is the dependent variable (y), and the adjustable
parameters are ∆ε and K. In the notation of the least squares program, Cl is the
variable x[i], ∆ε is the constant C[1] and K is the constant C[2].
To do the curve fitting, you can use the procedure "Nonlinear Least Squares
Curve Fitting with Microsoft Excel Solver" described early in this CD-ROM or you
can use the computer program on this CD-ROM.
To begin the least-squares procedure, we need estimates of ∆ε and K. For this
purpose, let's pretend that curve 5 corresponds to complete conversion of M to ML.
Therefore
AML = εML[ML]

0.494 ≈ εML[2.12 × 10-4 M] ⇒ εML ≈ 2.33 × 103 M-1. cm-1

From curve 0 we know εM = A/[M] = 0.859/2.12 × 10-4 = 4.05 × 103 M-1. cm-1.
Therefore, ∆ε = εML - εM ≈ -1.72 × 103 M-1. cm-1.
To estimate K, suppose that the conversion of M to ML for curve 1 is in
proportion to the absorbance change:
A - A 0.745 - 0.859
[ML] ≈  A1 - A 0 Cm ≈  0.494 - 0.859  (2.12 × 10-4) = 6.61 × 10-4 M
 5 0  
From the mass balance for metal, we estimate [M] = Cm - [ML] ≈ 1.46 × 10-4 M.
The mass balance for ligand gives [L] = Cl - [ML] ≈ 0.513 × 10-3 - 6.61 × 10-5 =
4.49 × 10-4 M. Our estimate of the equilibrium constant is therefore
[ML] 6.61 × 10 -4
K = [M][L] ≈ = 1.0 × 103
(1.46 × 10 -4)(4.49 × 10 -4)
Happy hunting! The values produced by your least-squares program should be
∆ε = -1 944 (±25) M-1. cm-1 and K = 829 (±35).
If you crave more, you can find spectrophotometric data for the sequence
M + L → ML → ML2 given by N. K. Kildahl, J. Chem. Ed. 1992, 69, 591. Try
deriving equations to fit these data with your least squares program and find the
formation constants K1 and K2.
 SP 30 CHAPTER 14: SUPPLEMENTARY PROBLEMS
FUNDAMENTALS OF ELECTROCHEMISTRY

S14-1. (a) Identify the oxidizing and reducing agents among the reactants below and write
a balanced half-reaction for each.
2S O2- + TeO2- + 2OH-
2 4 3 4SO2- + Te(s) + H O
3 2
Dithionite Tellurite Sulfite

(b) How many coulombs of charge are passed from reductant to oxidant when
1.00 g of Te is deposited?
(c) If Te is created at a rate of 1.00 g/h, how much current is flowing?

S14-2. Draw a picture of each of the following cells, showing the location of each chemical
species. For each cell, write an oxidation for the left half-cell and a reduction for
the right half-cell.
(a) Au(s) | Fe(CN)4- (aq), Fe(CN)3- (aq) || Ag(CN)- (aq), KCN(aq) | Ag(s)
6 6 2

(b) Pt(s) | Hg(l) | Hg2Cl2(s) | KCl(aq) || ZnCl2(aq) | Zn(s)

S14-3. Find the theoretical electrical storage capacity of cells that make use of the following
chemical reactions. Express your answer in ampere . hours per kilogram of
reactants, where 1 A. h provides 1 A for 1 h. Thus if consumption of 0.5 kg of
reactants produces 3 A. h, the storage capacity would be 3 A. h/0.5 kg = 6 A. h/kg.
Which cell produces the most electricity per kilogram, and which the least?
(a) Lead-acid battery: Pb + PbO2 + 2H 2SO4 → 2PbSO4 +2H 2O
(MW of reactants = 207.2 + 239.2 + 2 × 98.079 = 642.6.)
(b) Carbon-zinc dry cell: Zn + 2NH4Cl + 2MnO2 → ZnCl2(NH 3)2 + 2MnO(OH)
(MW of reactants = 346.25.)
(c) Nickel-cadmium cell: 2Ni(OH)2 + Cd(OH)2 → NiO(OH) + Cd + 2H2O
(MW of reactants = 331.84.)
(d) Sulfur-aluminum battery: 2Al + 3S + 3KOH + 3H2O → 2Al(OH)3 + 3KHS
(MW of reactants = 372.525.)
(e) Hydrogen-oxygen fuel cell: 2H2 + O2 → 2H2O (MW of reactants = 36.031)

S14-4. Which will be the strongest reducing agent under standard conditions
(all activities = 1): Se, Sn4+ , Cr 2+ , Mg2+ , or Fe(CN)46-?

S14-5. Use Le Châtelier's principle and half-reactions from Appendix H to find which of
the following become stronger reducing agents when the solution becomes more
basic. Which are unchanged, and which become weaker?
Cl2 Al H2S MnO2-
4 S2O2-
3
Chlorine Aluminum Hydrogen sulfide Manganate Thiosulate
 Chapter 14: Supplementary Problems SP 31

S14-6. Consider the cell

Pt(s) | H2(g, 0.100 atm) | H + (aq,pH = 2.54) || Cl-(aq, 0.200 M) | Hg 2Cl2(s) | Hg(l) | Pt(s)
(a) Write a reduction reaction and Nernst equation for each half-cell.
For the Hg2Cl2 half-reaction, E˚ = 0.268 V.
(b) Find E for the net cell reaction and state whether reduction will occur at the left-
or right-hand electrodes.

S14-7. Consider a circuit in which the left half-cell was prepared by dipping a Pt wire in a
beaker containing an equimolar mixture of Cr2+ and Cr3+ . The right half-cell
contained a Tl rod immersed in 1.00 M TlClO4.
(a) Use line notation to describe this cell.
(b) Calculate the cell voltage.
(c) Write the spontaneous net cell reaction.
(d) When the two electrodes are connected by a salt bridge and a wire, which
terminal (Pt or Tl) will be the anode?

S14-8. Write a balanced chemical equation (in acid solution) for the reaction represented by
the question mark below. Calculate E˚ for the reaction.
0.773 1.108 ?
NO3- NO2(g) HNO 2 NO
0.955

S14-9. Calculate E˚, ∆G˚, and K for each of the following reactions.
(a) Cu(s) + Cu2+ 2Cu+
(b) 2F2(g) + H 2O F2O(g) + 2H+ + 2F -

S14-10. A solution contains 0.010 0 M IO-3, 0.010 0 M I-, 1.00 × 10-4 M I-3, and pH 6.00
buffer. Consider the reactions
2IO-3 + I- + 12H + + 10e- I-3 + 6H 2O E˚ = 1.210 V
I- + 2e-
3 3I- E˚ = 0.535 V
(a) Write a balanced net reaction that can occur in this solution.
(b) Calculate ∆G˚ and K for the reaction.
(c) Calculate E for the conditions given above.
(d) Calculate ∆G for the conditions given above.
(e) At what pH would the concentrations of IO-3, I-, and I -3 listed above be in
equilibrium at 298 K?
 SP 32 Chapter 14: Supplementary Problems

S14-11. From the half-reactions below, calculate the solubility product of Mg(OH)2.
Mg2+ + 2e- Mg(s) E˚ = -2.360 V
Mg(OH)2(s) + 2e- Mg(s) + 2OH- E˚ = -2.690 V

S14-12. The standard free energy of vaporization of Cl2(aq) is ∆G˚ = -6.9 kJ/mol at 298 K.
Given that E˚ for the reaction Cl2(g) + 2e- 2Cl-(aq) is 1.360 V, find E˚ for the
reaction Cl2(aq) + 2e- 2Cl-(aq).

S14-13. Consider the cell S.H.E. || Ag(S2O3)32-(aq,0.010 M), S2O23-(aq,0.050 M) | Ag(s)

(a) Using the half-reaction Ag(S O )3- + e- Ag(s) + 2S O2-, calculate the cell voltage (E, not E˚).
2 3 2 2 3
(b) Alternatively, the cell could have been described with the half-reaction
Ag+ + e- Ag(s). Using the cell voltage from part a, calculate [Ag+ ] in the
right half-cell.
(c) Use the answer to part b to find the formation constant for the reaction
Kf
Ag+ + 2S O2- 2 3 Ag(S O )3- 2 3 2
Thiosulfate

S14-14. The following cell has a voltage of 1.018 V. Find Ka for formic acid, HCO2H.
Pt(s) | UO2+ (0.050 M), U4+ (0.050 M), HCO H(0.10 M), HCO Na(0.30 M)
2 2 2
|| 3+
Fe (0.050 M), Fe2+ (0.025 M) | Pt(s)

S14-15. For the following cell , the half-reactions can be written

Right half-cell: Pb2+ (right) + 2e- Pb(s)
Left half-cell: Pb2+ (left) + 2e- Pb(s)
(a) Given that Ksp for Pb(HPO4)(s) is 2.0 × 10-10, find [HPO 24-] in the left half-cell.
(b) If the measured cell voltage is 0.097 V, calculate Ksp for PbF 2(s).

- +
V

Pb Pb

Pb(HPO4 )(s) Precipitated

PbF2 (s)

Solution prepared from Prepared by mixing

25.0 mL of 0.124 M Na3 PO4 25.0 mL of 0.124 M Pb(NO3 )2
and 25.0 mL of 0.248 M HClO4 and 25.0 mL of 0.248 M KF
 Chapter 14: Supplementary Problems SP 33

S14-16. The monstrous cell below was set up. Then 50.0 mL of 0.044 4 M Na2EDTA was
added to the right-hand compartment and 50.0 mL of 0.070 0 M NaOH was added
to the left-hand compartment. The cell voltage leveled off at +0.418 V. Find the
formation constant for CuY2- (where Y = EDTA).
- +
V

Sb
Sb Cu
Sb 2 O3

100.0 mL of 0.015 2 M 100.0 mL of solution containing

nitrilotriacetic acid 1.37 mM Cu(EDTA)2- and
(a neutral compound, of course) 23.8 mM Ca(NO3 )2
buffered to pH 9.76

S14-17. Evaluate E˚' for the half-reaction CO2(g) + 2H + + 2e- CO(g) + H2O.

S14-18. Evaluate E˚' for the half-reaction CO2(g) + 2H + + 2e- HCO2H(aq).

S14-19. The standard reduction potential of anthraquinone,-2,6-disulfonate is 0.229 V.

O OH
SO3 - SO3-
+ -
+ 2H + 2e = Acidic
-O S -O S
3 3 protons
O OH

Anthraquinone-2,6-disulfonate

The reduced product is a diprotic acid with pK1 = 8.10 and pK2 = 10.52. Calculate
E˚' (pH = 7) for anthraquinone-2,6-disulfonate.