Hydronium Ions in

Solution and pH 21

21 :1

Ionization of Water; The pH Scale

Pure water ionizes slightly into hydronium and hydroxide ions:

It has been found by experiment that one liter of pure water contains only one ten millionth of a mole of hydronium ions and one ten millionth of a mole of hydroxide ions. A substance which contains more hydronium ions than hydroxide ions is acidic; a substance which contains more hydroxide ions than hydronium ions is basic; and a substance such as pure water which contains an equal number of hydronium ions and hydroxide ions is neutral. The ions are in equilibrium in pure water when the concentration of hydronium ions is 10-7 moles in each liter of water and the hydroxide ion concentration is also 10-7 moles per liter. In equation form:

+

1 liter of water at equilibrium 10-7 moles of 10-7 moles of

(55.6 moles) contains hydronium ions hydroxide ions

We can now write the equilibrium expression for water with the information just given and find an equilibrium constant for water. (Remember that the symbol [ ] means moles per liter.)

2HzO H30+ + OH-

[H30+] [OH-] Keq = [HzO][H20]

184

Hydronium Ions in Solution and pH 185

Since the ionization of water is very small in comparison with the total concentration of water (55.6 moles)", the concentration of water can be assumed to remain constant. If the concentration of water is constant, we can multiply both sides of the equation by this constant without destroying the relationship.

[H 0]2 X (K ) = [H 0]2 X ([HP+][OH-])

2 eq 2 [H20]2

Since both [H20] and Keq are constants, their product will also be constant. We call this constant the ion product constant of water and denote it by the symbol Kw. The ion product constant for water has been found to be 10-14 at room temperature.

K; = [HP+][OH-] = 10-14 Inspect this relationship and note that when:

[H30+] = 10-1, [H30+] = 10-13, [H30+] = 10-7,

the [OH-] = 10-13 the [OH-] = 10-1 the [OH-] = 10-7

This simple relationship has been used to construct what is called the pH scale which is used to indicate how acidic or basic a solution is. The pH scale ranges from 0 to 14. A pH of 7 is neutral; a pH of 1 is acidic; and a pH of 14 is basic.

The pH scale indicates the hydronium ion concentration. Another related scale, the pOH scale, is used to indicate the hydroxide ion (OH-) concentration. The relationship between the two can be seen in the chart. If you know the pll, simply subtract the pH value from 14 to change to the pOH scale.

Least acidic

pH +pOH= 14
[H30+] pH [OH-] pOH [H30+] [OH-]
10-1 1 10-13 13 10-14
10-2 2 10-12 12 10-14
10-3 3 10-11 11 10-14
10-4 4 10-10 10 10-14
10-5 5 10-9 9 10-14
10-6 6 10-8 8 10-14 Increasingly acidic

"You may wonder where the 55.6 moles came from. We are working with one liter of water which has a mass of 1000 g. You know that one mole of water has a mass of 18 grams. Therefore, one liter of water must contain

1000 g

18 g/mol : 55.6 moles of water.

186 Hydronium Ions in Solution and pH

Increasingly basic

10-7 7 10-7 7 10-14
10-8 8 10-6 6 10-14
10-9 9 10-5 5 10-14
10-10 10 10-4 4 10-14
10-11 11 10-3 3 10-14
10-12 12 10-2 2 10-14
10-13 13 10-1 1 10-14 Neutral

Least basic

Note that as the pH increases, the paH decreases and the product, [H30+] X [OH-], is always 10-14•

Table 21-1

Approximate pH of Some Common Substances

pH

1.0M HCI 0

0.1 M HCI 1.0

Stomach acid 2.0

Lemon 2.3

Vinegar 2.8

Carbonated beverage J.O

Orange 3.5

Tomato 4.2

Rainwater 6.0

Kw is a constant for all dilute aqueous solutions. Although the concentrations of H30+ and OH- may change when substances are added to water, the product of [H30+] and [OH-] remains the same.

pH

Milk

6.5 7.0 7.4 8.5 9.0

11.0 13.0 14.0

Pure water

Human blood Seawater

Household bleach Household ammonia 0.1 M NaOH

1.0M NaOH

Kw = [H30+][OH-] = 1.00 X 10-14

If an acid is added to a solution, the [H30+] increases and the [OH-] decreases. If a base is added, the [OH-] increases and H30+ decreases. Even in solutions which are acidic and contain a very large number of hydronium ions, a very small number of hydroxide ions exist.

To work problems involving pH and paH, you must translate from these two scales back to concentration of moles per liter. If you wish to prepare a solution of a specific pH, you must also know how many moles of hydronium ion must be present per liter. For the simpler problems, you will have no difficulty if you thoroughly understand the definitions of pH, paH, [H30+] and [OH-]. For the more complex problems, you must be able to manipulate logarithms and exponents.

We will use a neutral solution to show the relationship between the symbols and their relation to exponents and logarithms. A neutral solution contains 10-7 moles of hydronium ions per liter and 10-7 moles of hydroxide ions per liter.

Hydronium Ions in Solution and pH 187

[H30+] = 10-7 [OH-] = 10-7

pH=7 pOH=7

Note that the pH and pOH are simply the exponents of the ion concentrations without the negative signs. To translate into mathematical form, we must introduce logarithms because we are dealing with exponents.

pOH = -log[OH-]

Logs are used simply because they are exponents of ten and it is convenient to deal with hydronium ion concentrations in terms of powers of ten and scientific notation. (See the Appendix for a discussion on logs.)

Example 1 _

What is the pH and the pOH of a solution which contains 10-4 (the same as 1 X 10-4) moles of H30+ ions per liter?

Solving Process:

pH = -log [H30+]

= -log (1 X 10-4)

= -(log 1 + log 10-4) pH= -[0+(-4)]=4

Since pH + pOH = 14; pOH = 10

Example 2 _

Calculate the pOH and pH of a solution which contains 0.001 M NaOH. Assume 100% ionization.

Solving Process:

One hundred percent ionization means there is 0.001 mole OHper liter or,

[OH-] = 0.0.01 mole~ OH- = 1 X 10-3 moles OH-

liter solution liter solution

Substitute into the expression for pOH:

pOH = -log [OH-]

= -log (1 X 10-3)

= -(log 1 + log 10-3) pOH = -[0 + (-3)] = 3

Thus, the pOH is 3. Since pH + pOH = 14, the pH of this solution is 11.

188 Hydronium Ions in Solution and pH

Example 3 _

What is the pH of a solution which contains 1 X 10-5 mole of OHper liter?

Solving Process:

Find the [H30+] from the expression [H30+] X [OH-] = 1 X 10-14; then solve for the pH.

[H30+] X 1 X 10-5 = 1 X 10-14

[H 0+] = 1 X 10-14 = 1 X 10-9

3 1 X 10-5

pH = -log [H30+] = -log (1 X 10-9) = -(log 1 + log 10-9)

pH = - [0 + (- 9)] = 9

Example 4 _

Determine the pH and pOH of a solution which contains 0.0035 mole of H30+ per liter.

Solving Process:

pH = -log [H30+] = -log (3.5 X 10-3) = -(log 3.50 + log 10-3)

The logarithm table in the Appendix shows that the log of 3.5 is equal to 0.54.

pH = -[0.54 + (-3)] = 2.46

Solve for the pOH:

pH + pOH = 14.00

pOH = 14.00 - 2.46 = 11.54

Example 5 _

What is the pOH of a solution containing 0.042M KOH? Assume 100% ionization.

Solving Process:

Assume 100% ionization gives 0.042 mole OH- per liter. Therefore, the hydroxide ion concentration is 4.2 X 10-2 M.

pOH = -log [OH-] = -log (4.2 X 10-2) = -(log 4.2 + log 10-2)

Hydronium Ions in Solution and pH 189

From the logarithm table, the log 4.2 is equal to 0.62. pOH = -[0.62 + (-2)]

= 1.38

Example 6 _

What is the [H30+] in a solution which has a pH of 4.000?

Solving Process:

pH = -log [H30+] 4.000 = -log [H30+] -4.000 = log [H30+] antilog (-4.000) = [H30+]

1.000 X 10-4 = [H30+]

Example 7 _

Calculate the [H30+] of a solution which has a pH of 3.70.

Solving Process:

pH = -log [H30+]

- 3.70 = log [H30+]

Because the logarithm table does not give the mantissa for negative numbers, -3.70 is expressed as 0.30 - 4. From the log table, the antilog 0.30 is 2.0.

0.300 - 4 = log [H30+] 2.0 X 10-4 = [H30+]

Example 8 _

What is the [OH-] and the[H30+] of a solution if the pOH is 4.40?

Solving Process:

pOH = -log [OH-]

-4.40 = log [OH-]

Because the logarithm table does not give the mantissa for negative numbers, -4.4 is expressed as 0.600 - 5. From the log table, antilog 0.6 = 3.98.

0.600 - 5 = log [OH-] 3.98 X 10-5 = [OH-]

To solve for the [H30+], substitute into the equation.

190 Hydronium Ions in Solution and pH

[H30+] X [OH-] = 1.00 X 10-14

[H 0+] = 1.00 X 10-14 = 1.00 X 10-14

3 [OH-] 3.98 x 10-5

:= 0.25 X 10-9 = 2.5 X 10-10M

Problems

1. Calculate the pH and the pOH of solutions having the following concentration:

a. 0.00010 mole H30+ per liter

b. 0.010 mole OH- per liter

c. 1.0 X 10-5 mole OH- per liter

d. 1.0 X 10-2 mole H30+ per liter

2. Calculate the [H30+] of the following solutions:

a. pH = 3.0 b. pH = 6.0 c. pOH = 12.0

3. Calculate the [OH-] of the following solutions:

a. pOH = 11.0 b. pH = 4.0 c. pOH = 8.0

4. Calculate the pH and the pOH of solutions having the following concentrations. Assume 100% ionization. Remember that 1 mole of H2S04 produces 2 moles of H30+ ion.

a. 0.0025M NaOH d. 0.048M HCI

b. 0.0025MH2S04 e. 0.032MKOH

c. 0.075MH2S04 f. 0.00017MNaOH

21:2 Equilibrium Constants, Buffers, and pH

The acid - base equilibrium concepts (Chapter 20) can be used with the ideas discussed in this section. The constants Ka and Kb depend upon the temperature and are determined experimentally by measuring the pH of their solution.

Example 9 _

If the pH of a weak acid solution is 2.500 and the solution has a concentration of 0.1 DOOM, what is the Ka of the weak acid HA?

Solving Process:

Determine the H30+ concentration by substituting into the pH definition.

pH = -log [H30+] -2.500 = log [H30+]

Hydronium Ions in Solution and pH 191

0.500 - 3 = log [H30+] 3.16 X 10-3 = [H30+]

From the equation HA + H20 H30+ + A- and the calcula-

tion, [H30+] = [A-] = 3.16 X 10-3. Because each HA molecule that ionizes gives one H30+ and one A-, the original concentration of HA has decreased by the amount of H30+ formed. Thus, the HA concentration is 0.1000 - 0.00316 = 0.0968M. On substituting into the Ka expression:

[H30+][ A -] = (3.16 X 10-3)2 = 1.03 10-4

[HA] 0.0968 X

If the Ka or the Kb is known, the concentration of the ionic species can be calculated if the concentration is given. Once the concentration of the H30+ or the OH- is known, the pH or the pOH can be calculated.

Example 10 _

Determine the pH of an aqueous ammonia solution, if the [OH-] is equal to 3.00 X 10-3,

Solving Process:

Use the ion product expression for water and solve for the H30+,

«; = [H30+][OH-]

1.00 X 10-14 = [H30+] 3.00 X 10-3

[H 0+] = 1.00 X 10-14 = 0.333 X 10-11 = 3.33 X 10-12

3 3.00 X 10-3

Now use the definition of pH:

pH = -log H30+

= -log (3.33 X 10-12)

= -(log 3.33 + log 10-12) = -[0.522 + (-12)]

pH = 11.478

Consider a buffer solution consisting of sodium acetate and acetic acid. Most of the acetate ion is furnished by the soluble salt. The K; can be modified:

192 Hydronium Ions in Solution and pH

Example 11 _

A buffer solution contains 0.500 mole per liter each of acetic acid and sodium acetate. Determine the pH of the solution. The Ka of the acetic acid is 1.74 X 10-5•

Solving Process:

[H 0+] = K [acid] = [1.74 X 10-5] [0.500] = 1.74 10-5M

3 a [salt] [0.500] X

pH = -log H30+ = -log (1 .74 X 10-5)

= -(log 1.74 + log 10-5) = -[0.241 + (-5)]

pH = 4.759

Chapter Review Problems

5. Calculate the [H30+] and [OH-] of the following solutions:

a. pH = 2.500 c. pOH = 3.200 e. pH = 9.600

h. pOH = 5.800 d. pH = 4.700 f. pOH = 10.300

6. The approximate pH of some common substances is listed. Calcu-
late the pOH, the [H30+], and the [OH-]:
a. vinegar 2.8 e. soft drink 3.0
h. orange 3.5 f. tomato 4.2
c. rainwater 6.2 g. egg 7.8
d. seawater 8.5 h. milk of magnesia 10.5 7. The approximate pH of some common chemical solutions is listed.

Calculate the pOH, the [H30+], and the [OH-]:

a. O.lMHCI 1.00 d. 0.lMHzS04 1.20

h. 0.lMHCzH302 2.90 e. 0.lMNaHC03 8.40

c. O.lM NH3(aq) 11.10 f. O.lM NaOH 13.00

8. Find the pH of the solutions:

a. O.100M NH3(aq) Kb 1.74 X 10-5

h. O.100M HCzH30Z x, 1.74 X 10-5

c. 0.0500M HC2H302 s; 1.74 X 10-5

d. 0.750M HN02 tc, 4.50 X 10-4

e. 0.0100MH3B03 Kal 5.75 X 10-10

f. 0.00500M NH3(aq) tc, 1.74 X 10-5

9. Calculate the ionization constants of the following compounds:

a. 0.05MHCN pH 5.33 C. 0.10MNH3(aq) pHl1.12

b. O.lOMHC2H302 pH 2.87 d. 0.04MNH3(aq) pOH3.07

Titrations 22

Titration is an experimental procedure in which the unknown concentration of a known volume of solution is determined by measuring the volume of a solution of known concentration required to react completely with it.

The most common titrations involve the reaction of an acid solution with a basic solution. In laboratory work, volumes used are measured and the concentration of either the acidic or basic solution is known. An indicator is used to detect the endpoint, that is, an equivalent amount of standard solution has been added to the titrated solution. The reaction of the acid and base is termed a neutralization. The products of this reaction are a salt and water.

acid + base ~ salt + water

22:1 Titrations

The three types of titration reactions are: (1) an acid with a base to give a soluble salt and water, (2) a soluble salt with a second soluble salt to give a precipitate, and (3) an oxidizing material with a reducing material.

The reaction between a strong acid (HCI or HN03) and a strong base (NaOH) gives salts (NaCI and NaN03). Since these salts are products of strong acids and strong bases, the resulting solution is neutral.

For a strong acid/strong base titration, the pH at the endpoint is 7; but only a small amount of reagent causes a major pH change. The titration curve for the neutralization reaction is shown in Figure 22-1a. The indicator selected should change color in the pH range from about 4 to 10. Phenolphthalein is usually used since it is easy to detect visually a slight pink color from a colorless liquid. In the titration curves the letter E represents the endpoint.

Reaction between a strong acid (HCI, HN03, or H2S04) and a weak base (NH3) also produces salts (NH4Cl, NH4N03, and (NH4}zS04)' These salts hydrolyze to form slightly acidic solutions.

For a strong acid/weak base titration, the pH at the endpoint is less than 7 due to the hydrolysis reaction. The titration curve for this reaction

193

194 Titrotions

is shown in Figure 22-1b. Methyl orange can be used as an indicator because of the low pH region in which it changes color.

The reaction between a weak acid (HC2H302) and a strong base (NaOH) gives a salt (NaC2H302). Such salts hydrolyze to give a slightly basic solution.

For a weak acid/strong base titration, the pH at the endpoint is greater than 7 due to the hydrolysis reaction. The titration curve for this reaction is shown in Figure 22-1c. Any indicator changing color in the higher pH ranges could be used but phenolphthalein is most frequently used.

The concentration of the acid solution and basic solution will change slightly the position of the curves (especially at the start and completion of the titration) in relation to the pH.

Example 1 _

If 20.0 mL of a 0.300M solution of NaOH is required to neutralize 30.0 mL of a sulfuric acid solution, what is the molarity of the H2S04 solution?

Solving Process:

First write the balanced equation.

2NaOH + H2S04 ~ Na2S04 + 2H20

From the coefficients of the balanced equation, 2 moles of base are required for reaction with 1 mole of acid. From the problem, 20.0 mL of base are equivalent to 30.0 mL of acid.

M SO = 20.0 mL NaOH I 0.300.rnoJ.-.Nae1=t11 mol H2S04 = O. OOM

H2 4 30.0 mL H2S04 1 L NaOH 2..mGl-NaCll 1

Figure 22-la. 14

12

6 4

./ i--"""
/

Eql ivale hce J oint


j
- V 10 8

pH

2

o 10 20 30 40 50 60 70 80 90 100 mL NaOH added

Titrotions 195

14 Figure 22-1 b.

4 2

00 10 20 30 40 50 60 70 80 90 100

mL NHiaq) added

v
~
/"
/
Equ valer ee p pint

J
./ 12 10 8

pH

6

Figure 22-1c. 14

12 10

8

1/

Eql ivale nee I oint

)
- V
-
-: .... pH

10 20 30 40 50 60 70 80 90 100 m L NaOH added

Example 2 _

What volume in milliliters of 0.500M HN03 is required to neutralize 25.0 mL of a 0.200M NaOH solution?

Solving Process:

The balanced equation is

HN03 + NaOH ~ NaN03 + H20

From the coefficients of the balanced equation, 1 mole of acid will react completely with 1 mole of base. Start with the 25.0 mL of NaOH

196 Titrotions

solution. Convert the volume of base to moles using the concentration. Then convert to volume of acid using its concentration.

25.0~ I 0.200..JD..O.l...NBe1 ~ 11000 mL HN03 1000..DJ..L,..Ntte1J. (:Rol-NaOFf 0.500_woIIINeJ

= 10.0 mL HN03 soln

Example 3 _

In a laboratory experiment, 20.00 mL of NH3(aq) solution is titrated to the methyl orange endpoint using 15.65 mL of a 0.200M HCI solution. What is the concentration of the aqueous ammonia solution?

Solving Process:

NH3 + HCI ~ NH4CI

From the coefficients of the balanced equation, 1 mole of base reacts with 1 mole of acid. Also 20.00 mL of NH3 reacts with 15.65 mL of HCI.

M N ( 15.65 mL HCI 0.200 mol HCI 1 mol NH3

H3 aq) = 20.00 mL NH3 1 L HCI 1 mol HCI = 0.157M

Example 4 _

How many grams of KOH are required to neutralize 200.0 mL of a 4.00M solution of HN03?

Solving Process:

KOH + HN03 ~ KN03 + H20

From the coefficients of the balanced equation, 1 mole of base reacts completely with 1 mole of acid. From a formula mass calculation, 56.1 grams KOH equal 1 mole KOH.

200.0.m.b-+lN0314.00~ l~! 56.1 9 KOH - 9

1000.LJl.b...HNe3 1 llIel HN'6j J. llIell<Oi't - 44. 9

Example 5 _

How many liters of a 1.500M sulfuric acid solution are needed to neutralize completely 120.0 grams NaOH?

Solving Process:

2NaOH + H2S04 ~ Na2S04 + 2H20

From the coefficients of the balanced equation, 2 moles of NaOH react with 1 mole of H2S04, Start with 120.0 grams NaOH.

120.0_g-Wae1=t11~ 11.Jll.Ql.H~o; I 1 L H2S04 = 1.00 L 40.0..g..Naeti"" 2~ 1.50~

Titrotions 197

Example 6 _

In a laboratory experiment, a student neutralizes a 15.00 mL sample of vinegar (acetic acid solution) with 31.85 mL of a 0.400M NaOH solution. Calculate the following:

(a) the molarity of vinegar (acetic acid solution) (b) the grams of HC2H302 in 1 L of vinegar

(c) the percentage of acetic acid by mass in the vinegar (assume a density of 1.00 g/mL)

Solving Process:

(a) molarity of vinegar

31.85 mL NaOH

0.400 mol NaOH 1 mol vinegar =71~5.~0~0~m~L--v~in-e-g-a-rr-~1~L~N~a~07H~-+-1~m-071~N~a~O~H~

= 0.849M

HC H 0 0.849 mol HC2HP2 60.1 g HC2H302

grams 2 3 2 = ----:-:---=:.._::.-"=-+---:--=-~.::..-:~

1 L 1 mol HC2H302

(b)

1 L

(c) The percent mass is the number of grams of acetic acid in 100 grams of vinegar. Convert 51.0 grams HC2H302 per liter of vinegar to percent by using the density of vinegar.

percent mass HC2H302

51.0 g HC2H302 100°/0

----::-:---:----=---=--=-t-:-::---::- __ --+- __ -+-- /C = 5.1 0%

1 L vinegar 1

Example 7 _

What mass of barium chloride, BaCI2, is required to completely precipitate the barium sulfate, BaS04, from 35.00 mL of 0.200M H2S04?

Solving Process:

The balanced equation is

0.200~

1000~

= 1.46 g BaCI2

Problems

1. Calculate the unknown quantity for the complete neutralization of the following:

198 Titrotions
Acid Base
concentration volume concentration volume
a. 0.250MHCI 30.00mL ? NaOH 25.00mL
h. 0.500M H2SO4 ? 0.750MKOH 20.00mL
c. ? HN03 15.00mL 1.50MNH3 2S.00mL
d. 0.400MHN03 35.00mL 0.800MNaOH ? 2. What is the molarity of a NaOH solution if 25.00 mL is required to completely neutralize 40.00 mL of a 1.50M solution of H2S04?

3. Calculate the milliliters of a 0.600M solution of HN03 necessary to neutralize 28.55 mL of a 0.450M solution of KOH.

4. How many grams of calcium hydroxide, Ca(OHb are required to neutralize 52.68 mL of a 0.750M H2S04 solution?

5. How many milliliters of 0.500M NaOH are necessary to neutralize completely 20.00 mL of each of the following acids?

a. 0.150MHN03 c. 0.220MHCI

h. 0.250MH2S04 d. 0.450MH3P04

6. A titration of 15.00 mL of household ammonia NH3(aq) required 38.57 mL of 0.780M HC!. Calculate:

a. the molarity of the household ammonia h. the grams of NH3(aq) per liter of solution

c. the mass percentage of NH3(aq) in the solution. Assume a density of 0.950 g/mL for the solution

7. Determine the mass of the precipitate lead(II) sulfate, PbS04, which is produced by the reaction of 30.00 mL of 0.750M Pb(N03h with excess sulfuric acid.

8. How many milliliters of 1.50M HCI solution are required to react completely with a 0.500 gram sample of iron(II) sulfide ore if the ore contains 95.00% FeS?

22:2 Titrations with Normal Solutions

Titration problems can also be solved using the concentration expression normality and substituting into a mathematical equation.

Consider a reaction between a 1.00N HCI solution and a 1.00N NaOH solution. It is necessary to add equal volumes of the acid and base to have a complete reaction. An equal number of H30+ ions and OH- ions react to produce water. The other product, NaCI, is a salt of a strong acid and a strong base. The resulting solution is neutral.

The equivalent mass of a substance is that mass of material that will produce one mole of charge. One equivalent mass of hydrogen ions will

Titrotions 199

react with one equivalent mass of hydroxide ions. An equal number of equivalents of acid and equivalents of base will react completely to form a salt.

1. number of equivalents of solute

norma ity = ------=-::----:,-------- 1 L of solution

eq acid liters of acid

1 L solution

eq base liters of base

1 L solution

On substitution:

normality acid X volume acid = normality base X volume base or

Na X Va =Nb X ~

If any three values are known, the fourth value can be calculated.

For the factors to be equivalent, both volume terms must be liters or both must be milliliters. Do not mix liters and milliliters.

Acids or bases with one reacting hydrogen ion or hydroxide ion per formula unit contain 1 equivalent per mole. Acids or bases with two reacting hydrogen ions or hydroxide ions contain 2 equivalents per mole. Examples of the relationship between molarity and normality are

one reacting ion HCl

(1 eq = 1 mol) NaOH

2.00MHCl

= 2.00NHCl

O.300M NaOH = O.300N NaOH

two reacting ions H2S04

(2 eq = 1 mol)

Example 8 _

If 20.0 mL of a 3.00N solution of NaOH are required to neutralize 30.0 mL of a sulfuric acid solution, what is the normality of the H2S04?

Solving Process:

equivalents of acid = equivalents of base Na X Va = u, X Vb

Change milliliters to liters and then substitute:

N = 3.00N 0.0200~ = 2.00N

a 0.0300X

Example 9 _

What volume in milliliters of 0.500N HN03 is required to neutralize 25.0 mL of a 2.00N NaOH solution?

200 Titrotions

Solving Process:

milligram-equivalents acid = milligram-equivalents base

Na X Va = Nb X Vb

0.500N X Va = 2.00N X 25.0 mL

V = 2.00;( 25.00 mL = 100 mL

a 0.500ft

Example 10 _

How many grams of KOH are required to neutralize 200.0 mL of a 4.00N solution of HN03?

Solving Process:

For neutralization to be complete, the number of equivalents of acid must be equal to the number of equivalents of base. First, calculate the number of equivalents of acid. Then convert this answer to grams of KOH.

. 4.00 eq HN031 0.200~

equivalents HN03 = 1 X = 0.800 eq

equivalents acid = equivalents base 0.800~I.1-R=lell<e''156.1 g KOH ------t--,--:-:-:-=-:-:-=-i---'-:-:-=_:_:_ = 44.9 g KOH 1 ~ .1-mel I(OFt

Problems

9. What is the normality and the molarity of a phosphoric acid solution if 2S.00 mL of the solution is necessary to neutralize 30.00 mL of a O.SOON KOH solution?

10. In a laboratory experiment involving the neutralization of vinegar using O.SOON NaOH, the following data was collected:

Volume of vinegar Volume of base

Trial 1 10.00 mL 17.S9 mL

Trial 2 Trial 3

Calculate:

a. the normality of the vinegar in each trial

h. the grams of acetic acid per liter of vinegar

c. the mass percentage of HC2H302 in the vinegar. Assume a density of 1.00 g/mL

d. If the correct percentage is S.40%, which trial gave the best results? What is the percent error of this trial?

lS.27mL 20.14mL

28.39mL 36.S8mL

Chapter Review Problems

11. Calculate the unknown quantity required for the complete neutralization of the following:

Titrotions 201
Acid Base
concentration volume concentration volume
a. 0.lS0MHN03 32.70mL ? KOH 28.70mL
h. 0.3S0M H2SO4 26.50 mL 0.4S0MNaOH ?
c. O.SOOMHCl ? 1.00NKOH lS.00mL
d. ? H2SO4 lS.00mL O.SOOMNaOH 20.00mL
e. 0.2S0MHN03 2S.00mL 0.SOONNH3 ?
f. 0.SOOMH3P04 30.00mL ? 2S.00mL 12. Calculate the grams of NH3(aq) necessary to neutralize 30.00 mL of a 2.50M solution of HNO]"

13. How many milliliters of 0.7S0M sulfuric acid are needed to neutralize completely 20.00 grams of NaOH?

14. What volume of 0.2S0N H3P04 is required to neutralize 30.00 mL of a O.OSOOM Ba(OHh solution?

13. Determine the normality and the molarity of a sulfuric acid solution if 30.00 mL is used to neutralize 40.00 mL of a O.SOON KOH solution.

16. If 1.25 grams of pure CaC03 required 2S.S0 mL of a hydrochloric acid solution for complete reaction, calculate the normality of the acid.

17. How many milliliters of 0.2S0N AgN03 are required to precipitate all the chloride ion as AgCI in a solution made by dissolving a sample of rock salt which has a mass of 0.300 grams and is known to be 99.0% pure NaCI?

18. Hydrogen sulfide gas will react with a lead solution to give a precipitate of lead(II) sulfide, PbS. If H2S is bubbled into SO.O mL of a 0.2S0N Pb(C2H302h solution, calculate the following:

a. the grams of H2S required for complete reaction

h. the volume of H2S at STP required for complete reaction c. the grams of lead(II) sulfide produced

19. A common constituent of the "hardness" of water is often calcium carbonate. The amount of CaC03 is determined in the laboratory by titration with a standard acid such as HCI, producing water and CO2, A laboratory technician has just titrated a 100.0 mL sample of water containing CaC03 with O.lOON HCl and finds that 15.20 mL of acid were needed to reach the endpoint. Calculate the mass of CaC03 contained in exactly one liter of the water.

20. Potassium hydrogen phthalate, KHC8H404, is often used as a primary standard in the standardization of basic solutions. The potassium hydrogen phthalate, abbreviated KHP, reacts with a base to produce a salt and water. After preparing a solution of KOH which, you hope, is 0.100N, you decide to check the concentration

202 Titrotions

with KHP. You dissolve 0.200 grams of KHP in water and titrate with the 0.100N base. If the base is exactly O.IOON, how much base solution will be required?

19. -2.49°C, 84.1°C 23. 110 g/rnol
20. 28SC, 189°C 24. 43.5 g/mol
21. 160 g 25. 138 g/mol, CgHI002
22. 255 g 26. 218 g/mol, CIOH6N204
Chapter 20 1. a. 2Na + 2Hp ~ 2Na+ + H2 + 20H-

h. 6H+ + 2P043- + 3Mg2+ + 60H- ~ Mg3(P04)2 + 6H20

c. Ba2+ + SO/- ~ BaS04

d. -SMgH + 60H- + 6NH4 + + 2P043- ~

MgiP04)2 + 3NH3 + 6H20

e. 2Fe3+ + 3S2- ~ Fe2S3 g. 2AI + 3Cu2+ ~ 2AP+ + 3Cu

f. CO/- + 2H+ ~ CO2 + HP h. no reaction

2. a. 1.6 X 10-5 3. H30+ = 0.0042M 4.

h. 1.7 X 10-5 C2H302- = 0.0042M 5.

c. 6.16 X 10-10 Hc'H,O: = 1.0M

6. 0.56M 8. a. 2.54 X 103M

7. 0.035M h. 2.24 X 10-3M

0.42%

a. 7.90 X 10-4 h. 1.80 X 10-5

c. 1.85 X 10-5

d. 6.05 X 10-10

Chapter 21

1. a. pH 4, pOH 10 h. 1 X 10-6M 4. a. pH 11.4, pOH 2.6
h. pH 12, pOH 2 c. 1 X 1O-2M h. pH 2.30, pOH 11.70
c. pH 9, pOH 5 3. a. 1 X 10-IIM c. pH 0.82, pOH 13.18
d. pH 2, pOH 12 h. 1 X 1O-loM d. pH 1.32, pOH 12.68
2. a. 1 X 1O-3M c. 1 X 1O-8M e. pH 12.5, pOH 1.5
f. pH 10.2, pOH 3.8
5. a. H30+ = 3.162 X to-3M d. H30+ = 1.995 X to-5M
OH- = 3.162 X 10-12M OH- = 5.013 X 1O-loM
h. H30+ = 6.329 X to-9M e. H30+ = 2.512 X to-10M
OH- = 1.580 X 1O-6M OH- = 3.981 X lO-sM
c. H30+ = 1.585 X to-lIM f. H30+ = 1.995 X to-4M
OH- = 6.310 X 1O-4M OH- = 5.012 X 1O-IIM pOH H30+ OH- 8. a. 11.1
6. a. 11.2 1.6 X to-3M 6.3 X 1O-12M h. 2.88
h. 10.5 3.2 X 10-4M 3.2 X to-11M c. 3.03
c. 7.8 6.3 X to-7M 1.6 X to-8M d. 1.74
d. 5.5 3.2 X 10-9M 3.2 X 10-6M e. 5.62
11.0 1.0 X 10-3M 1.0 X 10-IIM f. 10.5
e. 4.4 X 10-10
f. 9.8 6.3 X 10-sM 1.6 X to-10M 9. a.
6.2 1.6 X 10-8M 6.3 X 10-7M h. 1.8 X 10-5
g. 1.8 X to-5
h. 3.5 3.2 X 10-IIM 3.2 X to-4M c.
d. 1.8 X 10-5
273 pOH H30+

7. a. 13.00 1.00 X lO-IM

b. 11.10 1.26 X 10-3M

c. 2.90 7.9 X 10-12M

d. 12.80 6.31 X 10-2M

e. 5.60 3.98 X 1O-9M

f. 1.00 1.0 X 10-13M

Chapter 22 _

OH-

1.00 X lO-I3M 7.94 X 10-12M 1.3 X 1O-3M 1.58 X 10-I3M 2.51 X lO-6M 1.00 X lO-IM

1. a. 0.300M 2. 2.40M b. 20.0 mL c. 3.60%

b. 15.0 mL 3. 21.41 mL c. 8.80 mL 7. 6.82 grams

c. 2.50M 4. 2.92 grams d. 54.0 mL 8. 7.21 mL

d. 17.5 mL 5. a. 6.00 mL 6. a. 2.0lM 9. 0.600NH3P04

10. a. 0.880N, 0.930N, 0.908N ,:-1 --:b"":"._3_4._2"*g-:-/L-=-:-:~_;0.;_20-0~M~H::_::+3P":'"O-.4 ....

b. 52.9g/L, 55.9g/L, 54.6g/L 11. a. 0.171M d. 0.333M

c. 5.29%, 5.59%, 5.46% b. 41.2 mL e. 12.5 mL

d. Trial 3, 1.11 % error c. 30.0 mL f. 1.80M

12. 1.28 grams 16. 0.980N

13. 333 mL 17. 20.3 mL

14. 12.0 mL 18. a. 0.213 grams

15. 0.667N.0.333M b. l40mL

Chapter 23 _

1. a. 1.50 X 10-16

b. 4.90 X 10-9

c. 4.14 X 10-11

d. 2.96 X 10-16 7.

e. 3.63 X 10-9

f. 2.82 X 10-13

2. a. 2.51 X 1O-18M

b. 3.97 X 1O-4M 8.

c. 2.61 X 1O-9M

d. 1.61 X 10-3M

3. a. 1.35 X 10-5M

b. 1.81 X 1O-9M

c. 1.81 X 10-8M

4. a. 1.11 X 10-2M

b. 5.50 X 1O-4M 9.

c. 5.50 X 10-2M

d. 3.71 X 1O-3M

5. a. 6.54 X 1O-5M

b. 7.00 X lO-loM

c. 1.06 X 1O-6M

6. a. 1.07 X 10-51 10.

b. 4.43 X 10-27 11.

c. 4.57 X 10-18 12.

274

c. 1.49 grams

19. 0.76g/L

20. 9.80mL

d. 1.53 X 10-72 13. a. 3.98 X 10-loM

e. 5.27 X 10-14 b. 3.54M

f. 1.00 X 10-25 c. 1.03 X 10-6M

a. 2.51 X 1O-17M 14. a. no, 2.50 X 10-7

b. 1.08 X 1O-5M b. yes, 2.25 X 10-11

c. 5.83 X 10-6M c. no, 1.08 X 10-30

d. 1.49 X 10-9M 15. 1.15 X 1O-8M

a. 8.91 X 1O-4M 16. 2.95 X 10-3 g/200 mL

b. 1.17X10-3M 17. yes

c. 3.07 X 10-2M 18. 3.83 grams

d. 2.14 X 1O-6M 19. 2.10 X 10-11 g/mL

e. 1.00 X lO-IM 20. yes, ion product

f. 6.91 X 10-7M = 4.17 X 10-7

g. 1.44 X 1O-4M 21. 7.94 X 10-8M

a. 3.94 X 10-2 mg/lOO mL

b. 1.72 X 10-3 mg/IOO mL

c. 2.10 X 10-6 mg 11 00 mL

d. 41.1 mgl100 mL 22. AgCl

e. 0.227 mgl100 mL 23. 5.4 X lO-sM,

f. 3.34 mg/ 100 mL 0.054%

AgI

PbS04

yes, PbC03