Segel, Biochemistry Calculations. Acid-base problems, solutions.

Fall 2012
11. Concentrated H2SO4 is 96% by weight and has a density of 1.84 g/mL. Calculate the
volume of concentrated acid required to make
(a) 750 mL of 1 N H2SO4
(b) 600 mL of 1 M H2SO4
(c) 1000 g of a dilute solution containing 12% H2SO4 by weight
(d) a solution containing 6.5 equivalents H2SO4 per liter
(e) a dilute H2SO4 solution of pH 3.8.
13. Calculate the weight of solid NaOH required to prepare
(a) 5 L of a 2 M solution
(b) 2 L of a solution of pH 11.5
(c) 500 mL of 62% w/w solution. The density of 62% NaOH soln is 1.15 g/mL.
14. How many mL of 0.12 M are required to neutralize exactly half of the OH- ions
present in 540 mL of 0.18 N NaOH?
24. Calculate the pH of a 0.2 M solution of an amine that has a pKa of 9.5.
26. How many mL of 0.1 M KOH are required to titrate completely 270 mL of 0.4 M
propionic acid?
27. How many mL of 0.2 M KOH are required to titrate completely 650 mL of 0.05 M
citric acid?
34. What is the pH of a solution containing 0.3 M Tris and 0.2 M Tris-HCl ? The pKa of
Tris-HCl is 8.1.
38. Describe the prep of 40 L of 0.02 M phosphate buffer, pH 6.9, starting from
(a) a 2 M H3PO4 soln and a 1 M KOH soln.
(b) a 0.8 M H3PO4 soln and solid NaOH
(c) a commercial concentrated H3PO4 soln and 1 M KOH
(d) 1 M solns of KH2PO4 and Na2HPO4
(e) solid KH2PO4 and K2HPO4
(f) solid K2HPO4 and 1.5 M HCl
(g) 1.2 M K2HPO4 and 2 M H2SO4
(h) solid KH2PO4 and 2 M KOH
(i) 1.5 M KH2PO4 and 1 M NaOH
(j) solid Na3PO4 and 1 M HCl
40. An enzyme-catalysed reaction was carried out in a solution buffered with 0.03 M
phosphate, pH 7.2. As a result of the reaction, 0.004 M acid was formed.
a) Find pH at the end of reaction
b) Find pH if no buffer were present
c) Write chemical equation showing how buffer resisted large change in pH.

Solutions
11. First it helps to express concentration in terms of molarity and normality.
96% w/w = 96 g H2SO4 / 100 g soln.
(96 g H2SO4 / 100 g soln) x (1.84 g soln / 1 mL soln ) x (1 mol H2SO4 / 98.073 g H2SO4 ) x (1000 mL / 1 L)

= 18.01 mol/L = 18 M H2SO4

Since there are two protons, there are two equivalents per mol:
18 mol / L (2 eq / mol) = 36 N
Calculate volume of concentrated acid to make
a) 750 mL of 1 N H2SO4
C1V1 = C2V2
36N (x mL) = 1 N (750 mL)
x = 20.8 mL
b) 600 mL of 1 M H2SO4
C1V1 = C2V2
18 M (x mL) = 1 M (600 mL)
x = 33.3 mL
c) 1000 g of dilute soln containing 12% H2SO4 by weight
1000 g soln (12 g H2SO4 / 100 g soln) = 120 g H2SO4 (1 mol / 98.073 g) = 1.22 mol H2SO4

C1V1 = C2V2 Instead of finding the molarity of the dilute solution, since you
know that molarity x Liters = moles, you can just substitute 1.22 mol for C2V2 .
18 M (x L) = 1.22 mol
x = 0.0678 L or 67.8 mL
d) 6.5 N H2SO4 solution
Assume 1 liter of 6.5 N solution so that C2V2 can be expressed in equivalents.
C1V1 = C2V2
36 N (x L) = 6.5 eq
x = 0.1805 L or 180.5 mL
e) A dilute H2SO4 solution pH 3.8
[H+] = 10-3.8 eq per liter. Assume 1 liter so that C2V2 can be expressed in equivalents.
C1V1 = C2V2
36 N (x L) = 10-3.8 equivalents (can also be expressed as 1.6 x 10-4 eq)
x = 4.4 x 10-6 L or 4.4 x 10-3 mL

13. Find weight of solid NaOH to prepare

a) 5 L of 2 M soln
5 L (2 mol / L) = 10 mol NaOH (40 g/ mol) = 400 g NaOH
b) 2 L of pH 11.5 soln
[H+] = 10-11.5
[OH-] = 10-2.5 = [NaOH]
10-2.5 mol/ L (2 L) = 2 x 10-2.5 mol NaOH (40 g/ mol) = 0.25 g NaOH
c) 500 mL of 62% wt soln, density 1.15 g/mL
(62 g NaOH / 100 g soln) x (1.15 g soln / 1 mL soln) = 0.713 g NaOH / mL soln

0.713 g/mL (500 mL) = 356.5 g NaOH

14. How many mL of 0.12 M H2SO4 to neutralize 50% of 540 mL of 0.18 N NaOH?
0.540 L x 0.18 N NaOH = 0.0972 eq NaOH x 50% = 0.0486 eq NaOH
0.12 M H2SO4 (2 eq/1mol) = 0.24 N H2SO4
C1V1 = C2V2
0.24 N (x L) = 0.0486 eq
x = 202.5 mL
24. Find pH of 0.2 M soln of an amine with pKa 9.5.
Only the pKa of a protonated amine would be in this region, but we have a
solution of a free amine, not an ammonium. So first find the association (base)
constant of the amine, the pKb:
pKa + pKb = pKw = 14
14 9.5 = 4.5 = pKb
Kb = [R3NH+] [OH-] / [R3N]
10-4.5 = x2 / 0.2 M
x = [OH-] = 2.5 x 10-3
[OH-][H+] = Kw
(2.5 x 10-3 ) [H+] = 10-14
[H+] = 4 x 10-12
pH = -log [H+] = 11.4
26. How many mL of 0.1 M KOH are required to titrate 270 mL of 0.4 M propionic acid?
(0.270 L)(0.4 M) = 0.108 mol H+
0.1 M KOH (x L) = 0.108 mol
x = 1.08 L
27. How many mL of 0.2 M KOH are required to titrate completely 650 mL of 0.05
M citric acid? Citric acid has 3 ionizable protons.
0.05 M (3 eq/mol) = 0.15 N citric acid
0.650 L (0.15 eq/L) = 0.0975 eq H+
0.2 M KOH (x L) = 0.0975 eq
x = 487.5 mL
34. What is the pH of a solution containing 0.3 M Tris and 0.2 M Tris-HCl ? The
pKa of Tris-HCl is 8.1.
pH = pKa + log [B] / [BH+]
pH = 8.1 + log [0.3] / [0.2]
pH = 8.28
38. Describe the prep of 40 L of 0.02 M phosphate buffer, pH 6.9, starting from
Before getting to trials (a)-(j), it helps to first figure out what this buffer looks like: what
species are in solution and how much of each? Based on the desired pH of 6.9, decide
which pKa of phosphoric acid would be useful to consider
H3PO4 to KH2PO4: pKa1 = 2.12
KH2PO4 to K2HPO4 : pKa2 = 7.21 <--K2HPO4 to K3PO4 : pKa3 = 12.32

When pH = pKa2 = 7.2, there is an equal ratio of KH2PO4 to K2HPO4.

When the pH is lower than pKa2, but not lower than the halfway point between
pKa1 and pKa2, there are still just these two species in solution, but there is more
KH2PO4 than K2HPO4. Now we can now find specifically how much of each will
be in solution at pH 6.9.
The buffer solution that we want has a given molarity and volume, so
40 L (0.02 M) = 0.8 mol total of KH2PO4 and K2HPO4.
To find the ratio of the two species,
pH = pKa + log [A-] / [HA]
6.9 = 7.2 + log [K2HPO4] / [KH2PO4]
-0.3 = log [K2HPO4] / [KH2PO4]
10-0.3 = 0.5 = [K2HPO4] / [KH2PO4]
So the ratio of K2HPO4 to KH2PO4 is 0.5 : 1 (or equivalently 1: 2) .
*Cross multiplying to express one species in terms of the other,
1 mol K2HPO4 = 0.5 mol KH2PO4
Now, to find the number of moles we need of each,
K2HPO4 + KH2PO4 = 0.8 mol
Substituting, 0.5 KH2PO4 + KH2PO4 = 0.8 mol
1.5 KH2PO4 = 0.8 mol
KH2PO4 = 0.53 mol
K2HPO4 = (0.5) KH2PO4 = (0.5) (0.53) = 0.27 mol K2HPO4
*Shortcut: The ratio 0.5 : 1 (which can also be expressed as 1 : 2) expresses parts
of a whole totalling 1.5 (or 3). That makes K2HPO4 a third of the total, and
KH2PO4 two thirds. One third of 0.8 mol is 0.27 mol K2HPO4. Two thirds of 0.8
mol is 0.53 mol KH2PO4.
(a) a 2 M H3PO4 soln and a 1 M KOH soln.
Starting with pure phosphoric acid requires neutralizing the fully protonated
species completely before considering anything else. So, its just a 1:1 titration 0.8 mol H3PO4 + 0.8 mol KOH gives 0.8 mol KH2PO4. Now we need to add just
enough KOH to give the mol ratio of KH2PO4 to K2HPO4 described above. Since
the KOH added to KH2PO4 simply becomes K2HPO4 and water, just add 0.27 mol.
Total KOH = 0.8 mol + 0.27 mol = 1.07 mol
Since we start with a 1 M KOH solution,
(1M)(x L) = 1.07 mol KOH
x = 1.07 L KOH
Since we start with a 2 M H3PO4 solution,
(2 M) (x L) = 0.8 mol H3PO4
x = 0.40 L or 400 mL H3PO4

(b) a 0.8 M H3PO4 soln and solid NaOH

Since 0.8 mol of phosphate solution is required, use one liter of 0.8 M H3PO4.
Since 1.07 mol NaOH is required to get the desired pH (see part a), 1.07 mol (40
g/ mol) = 42.7 g NaOH
(c) a commercial concentrated H3PO4 soln and 1 M KOH
This is a 14.8 M solution of H3PO4.
C1V1 = 0.8 mol H3PO4
(14.8M) (x L) =0.8 mol
x = 0.0545 L or 54.5 mL H3PO4 soln
For KOH, C1V1 = 1.07 mol. Using a 1 M soln, we need 1.07 L KOH
(d) 1 M solns of KH2PO4 and Na2HPO4
As shown earlier, we need 0.53 mol KH2PO4 and 0.27 mol Na2HPO4
Since we have 1 M solns of each, just take 530 mL and 270 mL respectively.
(e) solid KH2PO4 and K2HPO4
Multiply required moles (0.53 and 0.27, respectively) by the molecular weight of
each compound to find grams.
(f) solid K2HPO4 and 1.5 M HCl
0.8 mol (174 g/mol) = 139 g K2HPO4
To get 0.53 mol of the conjugate acid, use that amount of HCl:
C1V1 = 0.53 mol HCl
(1.5 M) (x L) = 0.53 mol
x = 0.355 L or 355 mL HCl soln
(g) 1.2 M K2HPO4 and 2 M H2SO4
C1V1 = 0.8 mol K2HPO4
(1.2 M) (x L) = 0.8 mol
x = 0.667 L or 667 mL K2HPO4 soln
To get 0.53 mol of the conjugate acid, use that amount of H2SO4 (but use
normality instead of molarity since two protons will dissociate per mol):
2 M H2SO4 = 4 N
4N (x L ) = 0.53 mol H2SO4
x = 133.25 mL H2SO4
(h) solid KH2PO4 and 2 M KOH
Start with 0.8 mol KH2PO4, multiply by molar mass.
Add 0.267 mol KOH:
2M (x L) = 0.267 mol
(i) 1.5 M KH2PO4 and 1 M NaOH
1.5M (x L) = 0.8 mol KH2PO4
1 M (x L) = 0.267 mol NaOH

(j) solid Na3PO4 and 1 M HCl

This is the reverse process of (a). Use 0.8 mol Na3PO4 , add 0.533 mol HCl

40. An enzyme-catalyzed reaction was carried out in a solution buffered with 0.03 M
phosphate, pH 7.2. As a result of the reaction, 0.004 M acid was formed.
a) Find pH at the end of reaction
First, find species ratios before reaction
At pH = pKa = 7.2, [HPO42-/ H2PO4-] = 1/1 .
Since we start with total conc. of 0.03 M, [H2PO4-] = [HPO42-] = 0.015 M
Acid from reaction neutralizes buffer base, turning it into its conjugate. Assuming
no change in volume, add 0.004 M to [H2PO4-] and subtract 0.004 M from [HPO42-].

pH = 7.2 + log (0.011/0.019) = 6.96

b) Find pH if no buffer were present
Assuming the acid produced in reaction is a strong acid,
pH = - log (0.004) = 2.4
c) Write chemical equation showing how buffer resisted large change in pH.
HPO42- + H3O+
H2PO4- + H2O -