Chemical Equilibria

1. The following equilibrium process has been studied at 230°C:

2NO(g) + O2(g) ⇋ 2NO2(g)
In one experiment, the concentrations of the reacting species at equilibrium are found to be [NO] = 0.0542
M, [O2] = 0.127 M, and [NO2] = 15.5 M. Calculate the equilibrium constant (Kc) of the reaction at this
temperature.
Solution:
2NO(g) + O2(g) 2NO2(g)
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( ) ( )

2. Given the following two equlibria:

NiCO3(s) → Ni2+(aq) + CO32-(aq) K1 = 6.6 x 10-9
HCO3 (aq) + H2O(l) → CO3 (aq) + H3O (aq)
- 2- + K2 = 4.8 x 10-11
Calculate the equilibrium constant for the following reaction.
NiCO3(s) + H3O+(aq) → Ni2+(aq)+ HCO3-(aq) + H2O(l)

Solution:
NiCO3(s) → Ni2+(aq) + CO32-(aq) K1 = 6.6 x 10-9
CO32-(aq) + H3O+(aq) → HCO3- (aq) + H2O(l) K2’ = 1/K2 = 1/(4.8 x 10-11)

NiCO3(s) + H3O+(aq) → Ni2+(aq)+ HCO3-(aq) + H2O(l) K3 = K1 x K2’

3. We examine the following reaction at 690 ºC.

CO2(g) + H2(g) → CO(g) + H2O(g).
At the equilibrium we find [CO2] = 1.5 x 10-4 M, [H2] = 2.2 x 10-4 M, [H2O] = 3.3 x 10-4 M and [CO] = 1.6 x
10-4 M. Calculate Kc for this equilibrium.
Solution:
[ ][ ]
[ ][ ]

( )( )
( )( )

4. Methanol (CH3OH) is manufactured industrially by the reaction

CO(g) + 2H2(g) ↔CH3OH(g)
The equilibrium constant (Kc) for the reaction is 10.5 at 220°C.
What is the value of Kp at this temperature?
Solution:

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 ( ) Should know how to derive
[( )( )]

5. Consider the following heterogeneous equilibrium:

CaCO3(s) ↔CaO(s) + CO2(g)
At 800°C, the pressure of CO2 is 0.236 atm. Calculate Kc for the reaction at this temperature.
Solution:

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[( )( )]

[( )( )]

6. Calculate the ionic strength of a solution consisting of 0.30 M NaCl and 0.20 M Na 2SO4.
Solution:

Solubility Equilibria
1. Calculate the solubility of Cu(OH)2 (97.54) in g/l. (Ksp = 2.2 E -20)
Solution:
Cu(OH)2 Cu2+ + 2OH-
I 0 0
Δ x x
E x x

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( )( )
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2. What is the molar solubility of Cr(OH)3 in a buffer solution whose pH is 12.00? (Ksp = 3 E -29)
Solution:
[OH-] = antilog(-pH) = antilog[-(14-12)] = 0.01 M
Cr(OH)3 Cr3+ + 3OH-

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 I 0 0
Δ x x
E x x
[ ][ ]
( )

3. A weight of AgCl corresponding to 1.0 millimole is shaken with 100 ml of water at 25 oC until
equilibrium is reached. What is the concentration of Ag + (107.87) in grams per milliliter in the
solution? (Ksp = 1.0 x 10-10)
Solution:
AgCl Ag+ + Cl-
I 0 0
Δ x x
E x x

[ ][ ]
( )( )

[ ]

[ ]

Acid-Base Equilibria
1. Calculate the pH of a 0.20 M CH3COOH solution. (The Ka of CH3COOH is 1.75 x 10-5)
CH3COOH CH3COO- + H+
I 0.20 0 0
Δ -x x x
E 0.20 - x x x

[ ][ ]
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( )( )

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2. Calculate the pH of a 0.10 M solution of sodium acetate. (The Ka of CH3COOH is 1.75 x 10-5)
Solution:
Sodium acetate is a strong electrolyte, so it dissociates completely in solution.
CH3COO- + H20 CH3COOH + OH-
I 0.10 0 0
Δ -x x x
E 0.10 - x x x

[ ][ ]
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3. Phenol is a monobasic acid with an ionization constant at 25 oC of 1.3 x 10-10. What is the pH of a 0.0010
M solution?
C6H5OH C6H5O- + H+
I 0.0010 0 0
Δ -x x x
E 0.0010 - x x x

[ ][ ]
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( )( )

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4. What is the pH of a solution containing both 0.20 M CH3COOH and 0.30 M CH3COONa?
Solution:
Sodium acetate is a strong electrolyte, so it dissociates completely in solution:
CH3COOH CH3COO- + H+
I 0.20 0.30 0
Δ -x x x
E 0.20 - x 0.30 + x x

[ ][ ]
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( )( )

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Or use Henderson hasselbach equation

5. Sodium hypochlorite (NaOCl, the active ingredient of almost all bleaches) was dissolved in a solution
buffered to pH 6.20. Find the ratio [OCl-]/[HOCl] in this solution. (pKa = 7.53 for HOCl)

Should know how to derive

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6. Calculate the volume of concentrated ammonia you would have to take to prepare 100 ml of a buffer at
pH 10.00 if the final concentration of salt is to be 0.200 M. (The Kb of NH3 is 1.75 x 10-5)

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 Solution:

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[ ( )]
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The molarity of concentrated ammonia is 14.8. Therefore,

7. The total carbon dioxide content (HCO3- + CO2) in a blood sample is determined by acidifying the sample
and measuring the volume of CO2 evolved with a Van Slyke manometric apparatus. The total concentration
was determined to be 28.5 mmol/L. The pH of blood at 37 ºC was determined to be 7.48. What is the
concentration of CO2 in the blood? (The pKa1 of blood at body temperature (37 ºC) is 6.10.)
Solution:

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[ ] [ ] (Equation 1)
[ ] [ ] (Equation 2)
[ ] [ ]
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(For items 8 – 9) Consider the addition of a 0.100 M NaOH solution (from a buret) to an Erlenmeyer flask
containing 25.0 mL of 0.100 M HCl. Calculate the pH

8. After the addition of 10.0 mL of 0.100 M NaOH to 25.0 mL of 0.100 M HCl.

Solution: (use moles not concentration!)

HCl + NaOH → NaCl + H2O

Initial (mmol) 2.5 1.0
Change (mmol) -1.0 -1.0
Final (mmol) 1.5 0

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[ ]

9. After the addition of 35.0 mL of 0.100 M NaOH to 25.0 mL of 0.100 M HCl.

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 Solution:
HCl + NaOH → NaCl + H2O
Initial (mmol) 2.5 3.5
Change (mmol) -2.5 -2.5
Final (mmol) 0 1.0

[ ]

(For items 10 – 12) Calculate the pH in the titration of 25.0 mL of 0.100 M acetic acid (Ka = 1.8 x 10-5) by
sodium hydroxide after the addition to the acid solution of
10. 10.0 ml of 0.1 M NaOH?
Solution:
CH3COOH + NaOH → CH3COONa + H2O
Initial (mmol) 2.5 1.0 0
Change (mmol) -1.0 -1.0 1.0
Final (mmol) 1.5 0 1.0

[ ]
[ ]

( )

11. 25 ml of 0.1 M NaOH?

Solution:
CH3COOH + NaOH → CH3COONa + H2O
Initial (mmol) 2.5 2.5 0
Change (mmol) -2.5 -2.5 2.5
Final (mmol) 0 0 2.5
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[ ]

Sodium acetate is a strong electrolyte, so it dissociates completely in solution.

CH3COO- + H20 CH3COOH + OH-
I 0.05 0 0
Δ -x x x
E 0.05 - x x x
[ ][ ]
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( )( )
( )
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( )

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12. 35 ml of 0.1 M NaOH?
Solution:
CH3COOH + NaOH → CH3COONa + H2O
Initial (mmol) 2.5 3.5 0
Change (mmol) -2.5 -2.5 2.5
Final (mmol) 0 1.0 2.5

Because OH- is a much stronger base than CH3COO-, we can safely neglect the hydrolysis of the
CH3COO- ions and calculate the pH of the solution using only the concentration of the OH- ions.

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If hydrolysis of CH3COO- ions is not neglected,

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Sodium acetate is a strong electrolyte, so it dissociates completely in solution.

CH3COO- + H20 CH3COOH + OH-

I 0.0417 0 0
Δ -x x x
E 0.0417 - x x x
[ ][ ]
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( )( )
( )
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For items 13 – 15
Calculate the pH of the resulting solution when 50 ml of 0.100 N NH3 was titrated with the following
volumes of 0.100 M HCl. (Kb = 1.75 x 10-5)
13. 5 ml of 0.100 M HCl added
NH3 + HCl → NH4Cl
Initial (mmol) 5 0.5 0
Change -0.5 -0.5 0.5
(mmol)
Final (mmol) 4.5 1.0 0.5

[ ]
[ ]

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 * +
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* +

14. At equivalence point

Solution:
NH3 + HCl → NH4Cl
Initial (mmol) 5 5 0
Change -5 -5 5
(mmol)
Final (mmol) 0 0 5

Ammonium chloride is a strong electrolyte, so it dissociates completely in solution.

NH4+ + H20 NH3 + H+

I 0.05 0 0
Δ -x x x
E 0.05 - x x x
[ ][ ]
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( )( )
( )
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15. 55 ml of 0.100 M HCl added

Solution:
NH3 + HCl → NH4Cl
Initial (mmol) 5 5.5 0
Change -5 -5 5
(mmol)
Final (mmol) 0 0.5 5

Because H+ is a much stronger acid than NH4+, we can safely neglect the hydrolysis of the
NH4+ ions and calculate the pH of the solution using only the concentration of the H+ ions.

[ ]
[ ]

16. Methylamine, CH3NH2, corresponds to a molecule of NH3, in which one hydrogen is replaced by the methyl
group. It has an ionization constant of 5.0 x 10-4, and can be determined by titration with acid. What is the
pH value at the equivalence point in the titration of 100 ml of 0.100 M aqueous solution of methylamine
with 0.250 M HCl?
Solution:

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 CH3NH2 + HCl → CH3NH3Cl
Initial (mmol) 10 10 0
Change -10 -10 10
(mmol)
Final (mmol) 0 0 10

[ ]
[ ]

CH3NH3+ + H20 CH3NH2 + H+

I 0.0714 0 0
Δ -x x x
E 0.0714 - x x x
[ ][ ]
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( )( )
( )
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( )

17. The Ka of a certain indicator is 2 x 10-6. The color of Hln is green and that of ln- is red. A few drops of the
indicator are added to a HCl solution, which is titrated against NaOH solution. At what pH will the indicator
change color?
Solution:

( )

18. A certain weak organic monobasic acid serves as an indicator. Assuming that the color change is seen
when two-fifths of the indicator has been converted to ions and at this point the pOH value of the solution
is 3.60, what is the ionization constant of the indicator?
Solution:

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19. A certain weak organic monoacidic base with an ionization constant of 2.0 x 10 -8 serves as an indicator in
a neutralization titration. An intermediate shade of color is obtained at pH 6.0. What percentage of the
indicator has been converted to ions at this point?
Solution:

Acid-Base Titrations
1. In standardizing a solution of HCl, it is found that 47.26 ml of the acid are equivalent to 1.216 g of pure
Na2CO3, 106 g/mol (methyl orange indicator). What is the normality of the acid?
Solution:

2. In standardizing a solution of NaOH against 1.431 g of potassium acid phthalate (KHP, 204.2 g/mol), the
analyst uses 35.50 ml of the alkali and has to run back with 6.12 ml of acid (1.00 ml = 0.004 g Na 2O, 62
g/mol). What is the normality of the NaOH solution?

3. A hydrochloric acid solution is standardized by titrating 0.2329 of primary standard Na 2CO3 (105.96) to a
methyl red end point by boiling the carbonate solution near the end point to remove the carbon dioxide. If
42.87 ml acid is required for the titration, what is its molarity?
Solution:

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4. If 60.0 ml of NaOH will neutralize 2.542 g of potassium tetroxalate (KHC 2O4·H2C2O4·2H2O ,254.1 g/mol),
and if 50 ml of HCl will neutralize 40.0 ml of this NaOH, what volume of 2.0 N HNO 3 should be added to
100.0 ml of the HCl in order to prepare a mixture which is 1.0 N as an acid?
Solution:

5. A mixture of 46.32 g of pure KOH (56.1) and 27.64 g of pure NaOH (39.99) is dissolved in water and
diluted to 1000 ml. What volume of 1.022 N HCl is required to neutralize 50.00 ml of the solution?
Solution:

6. If 30.0 ml of H2SO4 are required to neutralize 25.0 ml of 0.660 N KOH solution, to what volume should
200 ml of the acid be diluted with water in order for the resulting solution to be 0.5 N?
Solution:

7. What is the percentage of total acid expressed as acetic acid (CH3COOH, 60 g/mol) in a sample of vinegar
if 3.00 g of vinegar requires 20.50 ml of 0.1150 N KOH solution for an endpoint with phenolphthalein
indicator?
Solution:

For items 8 – 9
8. A solution of H2SO4 is standardized against a sample which has been previously found to contain 92.44 %
CaCO3 (100.06) and no other basic material. The sample weighing 0.7423 g is treated with 42.42 ml of
the acid and the excess acid then requires 11.22 ml of NaOH solution. If 1.00 ml of the acid is equivalent
to 0.9976 ml of the NaOH, what is the normality of H2SO4 solution?
Solution:

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 ( )

9. What is the normality of NaOH solution?

Solution:
( )

10. A sample of Rochelle salt (KNaC4H4O6·4H2O, 282.15 g/mol), after ignition to convert it to double
carbonate, is titrated with H2SO4, using methyl orange as an indicator. From the following data, calculate
the percentage purity of the sample. Wt. of sample = 0.9500 g; H 2SO4 used = 43.65 ml; NaOH used =
1.72 ml; 1.000 ml H2SO4 ≈ 1.064 ml of 0.1321 N NaOH.
Solution:

( )( )( )

11. A sample of crude ammonium salt weighing 1.000 g is treated with hot KOH solution. The NH 3 liberated is
collected in 50.00 ml of 0.50000 N acid, and the excess acid requires 3.12 ml of 0.2500 N NaOH for
neutralization. Calculate the percentage of NH3 in the sample.
Solution:

( )( )

12. A 50.00-mL sample of a citrus drink requires 17.62 mL of 0.04166 M NaOH to reach the phenolphthalein
end point. Express the sample’s acidity in terms of grams of citric acid, C 6H8O7, per 100 mL. (pKa1 =3.13;
pKa2 = 4.76; pKa3 = 6.40)
Solution:
( )( )
( )

13. A 0.2521 g sample of an unknown weak acid is titrated with 0.1005 M solution of NaOH, requiring 42.68
ml to reach the phenolphthalein end point. Which of the following compounds is most likely to be the
unknown weak acid?
A. Ascorbic acid
B. Malonic acid (C3H4O4) C. Succinic acid (C4H6O4) D. Citric acid (C6H8O7) –
(C6H8O6) –
– diprotic – diprotic triprotic
monoprotic

Solution:

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 Ascorbic acid (C6H8O6) – Malonic acid (C3H4O4) – Succinic acid (C4H6O4) Citric acid (C6H8O7) –
Acid triprotic
monoprotic diprotic – diprotic

EW

14. Tartaric acid, H2C4H4O6, has two acidic hydrogens. The acid is often present in wines and precipitates from
solution as the wine ages. A solution containing an unknown concentration of the acid is titrated with
NaOH. It requires 22.62 ml of 2.000 M NaOH solution to titrate both acidic protons in 40.00 ml of the
tartaric acid solution. Calculate the molarity of the tartaric acid?
Solution:

15. A mixture contains Na2CO3, NaOH and inert matter. A sample weighing 1.500 g requires 28.85 ml of 0.500
N HCl to reach a phenolphthalein endpoint, and an additional 23.85 to reach a methyl orange endpoint.
What are the percentages of Na2CO3 and NaOH?
Solution:
( )( )

[( )( )] ( )

16. A sample is known is known to consist of NaOH (40 g/mol) or NaHCO3 (84 g/mol), or Na2CO3 (106 g/mol)
or possible compatible mixtures of these, together with inert matter. With methyl orange, a 1.10 g sample
requires 31.4 ml of HCl (of which 1.00 ml ≈ 0.0140 g CaO, 56 g/mol). With phenolphthalein, the same
weight of sample requires 13.3 ml of the acid. Calculate the percentage of inert matter in the sample.
Solution:

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 ( )( ) ( )( )( )

For items 17 – 18
17. A sample consisting of Na2CO3 (105.96), NaOH (39.99) and inert matter weighs 1.179 g. It is titrated with
0.300 N HCl with phenolphthalein as the indicator, and the solution becomes colorless after the addition
of 48.16 ml. Methyl orange is then added and 24.08 ml more of the acid are needed for the color change.
What is the percentage of NaOH?
Solution:
( )( )| |

18. What is the percentage of Na2CO3?

Solution:
( )| |

19. What weight of BaCO3 (197.33 g/mol) should be added to 1.00 g of Li2CO3 (73.88 g/mol) so that the
mixture will require the same volume of standard acid for neutralization as would the same weight of
CaCO3 (100.1 g/mol)?
Solution:

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20. The purity of a pharmaceutical preparation of sulfanilamide, C6H4N2O2S (168.18), can be determined by
oxidizing the sulfur to SO2 and bubbling the SO2 through H2O2 to produce H2SO4. The acid is then titrated
with a standard solution of NaOH to the bromothymol blue end point, where both of sulfuric acid’s acidic
protons have been neutralized. Calculate the purity of the preparation, given that a 0.5136-g sample
required 48.13 mL of 0.1251 M NaOH.
Solution:
( )( )( )( )

Kjeldahl Analysis
1. A 7.279 g sample of meat was analyzed for its nitrogen content using Kjeldahl Method. Upon
digestion, the ammonia liberated was collected in 250 ml of 0.855 H 3BO3. The resulting solution was
titrated with 37.25 ml of 0.3122 M HCl. Determine the % protein in the sample using 6.25 as a factor
for meat products.
Solution:
( )( )( )( )

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 2. A sample of alfalfa meal weighing 2.0 g is analyzed by Kjeldahl method for the percentage of nitrogen.
The liberated NH3 is caught in a solution of H3BO3, and 8.23 ml of HCl are required in the subsequent
titration. A sample of pure (NH4)2SO4 (132.12) weighing 0.61 g is treated with excess NaOH and the
liberated NH3 (17.04) is also caught in H3BO3. The resulting solution requires 20 ml of the acid for
titration. Calculate the percentage of protein in the sample using 6.25 as the factor.
Solution:

( )
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3. The amount of protein in a sample of cheese is determined by a Kjeldahl analysis for nitrogen. After
digesting a 0.9814-g sample of cheese, the nitrogen is oxidized to NH4+, converted to NH3 with
NaOH, and distilled into a collection flask containing 50.00 mL of 0.1047 M HCl. The excess HCl is
then back titrated with 0.1183 M NaOH, requiring 22.84 mL to reach the bromothymol blue end point.
Report the %w/w protein in the cheese given that there is 6.38 g of protein for every gram of nitrogen
in most dairy products.
Solution:
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4. A sample containing the amino acid alanine, CH3CH(NH2)COOH, plus inert matter is analyzed by
Kjeldahl method. A 2.00 g sample is digested, the ammonia is distilled and collected in 50.0 ml of
0.150 M H2SO4, and a volume of 9.0 ml of 0.100 M NaOH is required for back titration. Calculate the
percent alanine in the sample.
Solution:

( )
( )( )( )( )

5. The percentage of protein in most food products is found arbitrarily by multiplying the percentage of
nitrogen by the factor 6.25. A sample of meat scrap weighing 2.0 g is digested with concentrated
H2SO4 plus a catalyst until the nitrogen in the material is converted to NH4SO4. NaOH liberates NH3
which is absorbed in 50 ml of dilute H2SO4, and the excess acid requires 22.14 ml of 0.6190 N NaOH.
A separate 50 ml portion of the H2SO4 is neutralized by 40.23 ml of the NaOH titrating solution.
Calculate the percentage of protein in the sample.
Solution:

( )| |

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 Redox Titrations

For items 1 – 2
1. A sample of pyrolusite (MnO2, 86.92 g/mol) weighing 0.6 g is treated with 0.7058 g of dissolved As 2O3
(197.81 g/mol) in the presence of acid. The excess As(III) requires 23.95 ml of KMnO 4, of which 1.0
ml ≈ 0.03038 g FeSO4·7H2O, 277.94 g/mol). What is the oxidizing power of the sample in terms of
percentage MnO2?
Solution:

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2. How many grams of Na2C2O4 (133.96) in presence of acid are theoretically required to bring about the
same reduction in 0.600 g of the pyrolusite without leaving an excess of oxalate?
Solution:
( )
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3. A 0.50 g of sample of chromite (Cr2O3, 151.95 g/mol) is fused with Na2O2, leached with water, and
acidified. The Cr is reduced by adding 2.78 g of FeSO4·7H2O (277.94 g/mol) crystals. The excess
ferrous ions then require 10.0 ml of K2Cr2O7, and 1.0 ml K2Cr2O7 ≈ 0.0160 g Fe2O3 (159.67 g/mol).
What is the percentage of Cr (51.99 g/mol) in the chromite?
Solution:

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4. A sample of chromite weighing 0.2000 g is fused with Na2O2 leached and acidified. To the solution is
added a certain weight of FeSO4·7H2O (277.94 g/mol) crystals, which is in excess of that required to
reduce the Cr(VI) present. The excess ferrous sulfate is titrated with K 2Cr2O7 (1.000 ml = 0.005585 g
Fe, 55.85 g/mol), and 10.10 ml are used, but it is necessary to back titrate with 0.2000 ml of a
ferrous solution containing 19.60 g of FeSO4·(NH4)2SO4·6H2O (392.05 g/mol) per liter. If the
percentage of Cr2O3 (151.95 g/mol) in the ore is 50.66%, what weight of FeSO4·7H2O was added?
Solution:

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 ( )

( )

* ( )+ | |
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5. What is the percentage of Cr (51.99) in a sample of chromite if a 0.500 g sample after fusion in the
regular way is treated with 50.0 ml of 0.12 N ferrous ammonium sulfate and the excess requires
15.05 ml of K2Cr2O7 (1.00 ml ≈ 0.006 g Fe, 55.85 g/mol)?
Solution:

( )| |

6. A sample of magnetite (impure Fe3O4) is completely decomposed and oxidized by fusion with Na2O2.
The mass is then leached with water and acidified. The total Fe is determined by reduction with SnCl 2,
destroying the excess Sn(II), and titrating with ceric sulfate. If 30.0 ml of 0.10 N solution are required
in the titration, what weight of Fe3O4 (231.51) is present in the sample?
Solution:
( )| |

7. What is the percentage of Sb (121.76 g/mol) in a 0.25 g sample of stibnite if 20.83 ml of I 2 are used
in the final titration and each milliliter of the I2 is equivalent to 0.004495 g of As (74.92 g/mol)?
Solution:

( )| |

8. What weight of CuS (95.6 g/mol) ore should be taken for analysis so that when Cu is determined
iodimetrically using 0.05 N Na2SO3, the buret reading will be two thirds the percentage of CuS in the
ore?
Solution:
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 9. Titrating with 0.05 N I2, what weight of stibnite should be taken so that the percentage of Sb 2S3
(339.7) in the sample will be 1.5 times the buret reading?
Solution:
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10. A 200 ml water sample was analyzed by Winkler Method. If 8 ml of 0.02 M Na 2S2O3 was used for
titration, determine ppm O2 in the water sample.
Solution:
( )| |( )

11. A 5.00 ml of brandy was diluted to 1.000 L in a volumetric flask. The ethanol in a 25 ml aliquot of the
diluted solution was distilled into 50.00 ml of 0.02000 M potassium dichromate and oxidized with
heating. After cooling, 20.00 ml of 0.1253 M Fe2+ was pipetted into the flask. The excess Fe2+ was
then titrated with 7.46 ml of the standard K2Cr2O7 to end point. Calculate the percent ethanol in the
brandy.
Solution:

[ ( )] | |

Precipitation Titrations
1. A mixture of LiCl (42.39 g/mol) and BaBr2 (297.15 g/mol), weighing 0.600 g is treated with 45.15
ml of 0.2017 N AgNO3, and the excess is found to require 25 ml of 0.1 N KCNS solution for titration,
using ferric alum as indicator. What is the percentage of BaBr2 in the sample?
Solution:

( )
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For items 2 – 3
A sample containing KCN weighs 0.4 g and requires 16 ml of 0.125 M AgNO 3 to obtain a faint
permanent turbidity.
2. What is the percentage of KCN (65.12 g/mol) in the sample?
Solution:
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 3. If the sample also contains 10.0% KCl (74.55 g/mol), what volume of the AgNO 3 would be required
to precipitate the cyanide and chloride completely?
Solution:

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Complexometric Titrations
1. A nickel ore weighing 1.2 g is analyzed by the volumetric method. The ammoniacal solution is treated
with 48.00 ml of solution containing 0.014 g of KCN (65.12 g/mol) per milliliter, and the excess
cyanide requires 0.5 ml of AgNO3 (169.85g/mol) solution (containing 0.0125 g AgNO3 per ml).
Determine the percentage of Ni (58.69 g/mol) in the ore.
Solution:

( )| |

2. The concentration of a solution of EDTA was determined by standardizing against a solution of Ca 2+

prepared from the primary standard CaCO3. A 0.4071-g sample of CaCO3 (100.06) was transferred to
a 500-mL volumetric flask, dissolved using a minimum of 6 M HCl, and diluted to volume. A 50.00-mL
portion of this solution was transferred into a 250-mL Erlenmeyer flask and the pH adjusted by adding
pH 10 NH3–NH4Cl buffer containing a small amount of Mg2+–EDTA. After adding calmagite as a visual
indicator, the solution was titrated with the EDTA, requiring 42.63 mL to reach the end point. Report
the molar concentration of the titrant (EDTA).
Solution:

3. Ni2+ can be analyzed by a back titration by using standard Zn 2+ at pH 5.5 with xylenol orange indicator.
A solution containing 25.00 ml of Ni2+ in dilute HCl is treated with 25.00 ml of 0.05283 M Na 2EDTA.
The solution is neutralized with NaOH, and the pH is adjusted to 5.5 with acetate buffer. The solution
turns yellow when few drops of indicator are added. Titration with 0.02299 M Zn 2+ requires 17.61 ml
to reach the red endpoint. What is the molarity of Ni2+ in the unknown?
Solution:

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 4. What is the percentage of Ni (58.69) in an ore if, when analyzed by the cyanide method, 20 ml of KCN
solution (containing 0.10 millimole of KCN per milliliter) and 1.50 ml of AgNO 3 (containing 0.20
millimole per milliliter) are used? Wt. of sample taken = 0.25 g
Solution:
( )| |

For items 6 – 7
A 50.0-mL solution containing Ni2+ and Zn2+ was treated with 25.0 mL of 0.0452 M EDTA to bind all
the metal. The excess unreacted EDTA required 12.4 mL of 0.0123 M Mg 2+ for complete reaction. An
excess of the reagent 2,3-dimercapto-1-propanol was then added to displace the EDTA from zinc.
Another 29.2 mL of Mg2+ were required for reaction with the liberated EDTA.
5. Calculate the molarity of Ni2+ in the original solution.
Solution:

( )

6. Calculate the molarity of Zn2+ in the original solution.

Solution:

7. Copper is saltwater near the discharge of a sewage treatment plant is determined by first separating
and concentrating it by solvent extraction of its dithizone chelate at pH 3 into methylene chloride and
then evaporating the solvent, ashing the chelate to destroy the organic portion, and titrating copper
with EDTA. Three 1-L portions of the sample are each extracted with 25 ml portions off the methylene
chloride, and the extracts are combined in a 100 ml volumetric flask and diluted to volume. A 50 ml
aliquot is evaporated, ashed, and titrated. If the EDTA solution has a CaCO 3 (100.06) titer of 2.69
mg/ml and 2.67 ml is required for titration of copper, what is the concentration of copper (63.54) in
seawater in parts per million?
Solution:

( )| |

8. An alloy of chromel containing Ni (58.69), Fe (55.85), and Cr (51.99) was analyzed by a complexation
titration using EDTA as the titrant. A 0.7176-g sample of the alloy was dissolved in HNO3 and diluted to
250 mL in a volumetric flask. A 50.00-mL aliquot of the sample, treated with pyrophosphate to mask
the Fe and Cr, required 26.14 mL of 0.05831 M EDTA to reach the murexide end point. A second
50.00-mL aliquot was treated with hexamethylenetetramine to mask the Cr. Titrating with 0.05831 M
EDTA required 35.43 mL to reach the murexide end point. Finally, a third 50.00-mL aliquot was

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 treated with 50.00 mL of 0.05831 M EDTA, and back titrated to the murexide end point with 6.21 mL
of 0.06316 M Cu2+. Report the weight percent of Fe, Ni and Cr in the alloy.
Solution:

Gravimetric Analyses

1. If a sample of silver coin weighing 0.25 g gives a precipitate of AgCl (143.32) weighing 0.2991 g,
what is the percentage Ag (107.87 g/mol) in the coin?
Solution:
| |

2. What weight of pyrite (impure FeS2, 119.97 g/mol) in grams should be taken so that the number
of centigrams of precipitated BaSO4 ( 233.35 g/mol) will be twice the percentage of FeS2?
Solution:
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3. A mixture of BaO (153.33) and CaO (56.08) weighing 2.2120 g is transformed into mixed sulfates
weighing 5.023 g. Calculate the weight in grams of BaO in the mixtures.
Solution:
( )

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 | | | | ( )

4. A precipitate of AgCl (143.32 g/mol) + AgBr (187.78 g/mol) weighs 0.8132 g. On heating a
current of Cl2, the AgBr is converted to AgCl and the mixture loses 0.145 g. Find the percentage of
Cl (35.45 g/mol) in the original sample.
Solution:
( )
| | ( )

| |

5. A certain volume of NH4OH (sp. gr. 0.960, containing 9.91% NH3 by weight) is required to
precipitate the Al (26.98 g/mol) as Al(OH)3 (77.98 g/mol) from a 2.00 g sample of
KAl(SO4)2·12H2O (474.24 g/mol). What would be the precipitate weigh after ignition?
Solution:
( ) ⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗⃗

( ) | |
( )

6. A mixture of AgCl (143.32) and AgI (234.77), on being heated in a current of Cl2, is converted
entirely into AgCl and is found to have lost 6.00% of its weight. What is the percentage Cl (35.45)
in the original mixture?
Solution:
( )

| | ( )

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 7. What weight of impure ferrous ammonium sulfate should be taken for analysis so that the
number of centigrams of BaSO4 (233.35) obtained will represent five times the percentage of S
(32.06) in the sample?
Solution:
( )| |

8. An impure sample of Na3PO3 (147.91) weighing 0.1392 g was dissolved in 25 mL of water. A

solution containing 50 mL of 3% w/v mercury(II) chloride, 20 mL of 10% w/v sodium acetate and
5 mL of glacial acetic acid was then prepared. The solution containing the phosphite was added
dropwise to the second solution, oxidizing PO33– to PO43– and precipitating Hg2Cl2. After digesting,
filtering, and rinsing, the precipitated Hg2Cl2 (472.08) was found to weigh 0.4320 g. Report the
purity of the original sample as %w/w Na3PO3.
Solution:

| |

For items 9 – 11
A sample of soluble salt weighs 1.2 g and contains chloride, bromide and iodide. With AgNO3, a
precipitate is obtained which weighs 0.4500 g. On heating this precipitate with Cl2 gas, the AgBr
(187.78) and AgI (234.77) are converted to AgCl (143.32), and the precipitate then weighs
0.3300 g. A similar sample, when treated with palladous chloride, precipitates only PdI2 (360.2),
and this precipitate weighs 0.0900 g.

9. Find the approximate percentage of chlorine (35.45) in the sample.

Solution:
( )

| | | | ( )

| | ( )

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 10. What is the percentage bromine (79.91) in the sample?
Solution:
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11. What is the percentage iodine (126.90) in the sample?

Solution:
| |

12. A mixture containing only FeCl3 (162.2) and AlCl3 (133.33) weighs 5.95 g. The chlorides are
converted to the hydrous oxides and ignited to Fe2O3 (159.67) and Al2O3 (101.93). The oxide
mixture weighs 2.62 g. Calculate the percent Fe (55.85) and Al (26.98) in the original mixture.
Solution:
( )

| | | | ( )

| |

| |

13. A 523.1 mg sample of impure KBr (119.01) is treated with excess AgNO3 (169.85) and 814.5 mg
AgBr (187.78) is obtained. What is the purity of the KBr?
Solution:
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 14. The aluminum content of an alloy is determined gravimetrically by precipitating it with 8-
hydroxyquinoline (oxine) to give Al(C9H6ON)3. If a 1.021 g sample yielded 0.1862 g of precipitate,
what is the percent aluminum in the alloy?
Solution:
( ) | |
( )

For items 15– 16

Long ago, a workman at a dye factory fell into a vat containing hot, concentrated sulfuric and
nitric acids. He dissolves completely! Because nobody witnessed the accident, it was necessary
to prove that he fell in so that the man’s wife could collect his insurance money. The man weighs
70 kg, and a human body contains approximately 6.3 parts per thousand (mg/g) phosphorus. The
acid in the vat was analyzed for phosphorus to see whether it contained a dissolved man.
15. The vat contained 8.00 x 103 L of liquid, and a 100.00-ml sample was analyzed. If the man did
fell into the vat, what is the expected quantity of phosphorus (30.97) in 100.0 ml?
Solution:

16. The 100.0 ml sample was treated with a molybdate reagent that precipitated ammonium
phosphomolybdate, (NH4)3[P(Mo12O40)]·12H2O. This substance was dried at 110 ⁰C to remove
waters of hydration and heated to 400 ⁰C until it reached the constant composition P2O5·24MoO3
(3596.46), which weighed 0.3718 g. When a fresh mixture of the same acids (not from the vat)
was treated in the same manner, 0.0331 g of P2O5·24MoO3 was produced. How much
phosphorus was present in the 100.0 ml sample?
Solution:
( ) | |

Analysis of Minerals
1. A sample of feldspar weighing 2.0 g is decomposed by the J.L. Smith method and subsequently yields
a mixture of NaCl (58.44 g/mol) and KCl (74.55 g/mol) weighing 0.2558 g. This mixture is dissolved in
water and 35.0 ml of 0.10 N AgNO3 solution are added. The filtrate from the resulting precipitate then
requires 0.92 ml of 0.02 N KCNS solution to give a red color with ferric ions. Calculate the percentage
K (39.10 g/mol) and K2O (94.19 g/mol) in the feldspar.
Solution:

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 | |

| |

2. A mixture of NaCl (58.44) and KCl (74.55) from 0.50 g of feldspar weighs 0.15 g, and after
dissolving in water, requires 22.71 ml of 0.1012 N AgNO3 for complete precipitation of the
chloride ions. What is the percentage of Na2O (61.97) in the feldspar?
Solution:

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