Problems http://edugen.wiley.com/edugen/courses/crs1900/rc/voet9301c02/dm9ld...

1. Identify the potential hydrogen bond donors and acceptors in the following molecules:

Answer:

(a) Donors: NH1, NH2 at C2, NH9; acceptors: N3, O at C6, N7.
(b) Donors: NH1, NH2 at C4; acceptors: O at C2, N3.
(c) Donors: group, OH group; acceptors: COO– group, OH group.

2. Occasionally, a C—H group can form a hydrogen bond. Why would such a group be more likely to be a
hydrogen bond donor group when the C is next to N?

Answer:

A protonated (and therefore positively charged) nitrogen would promote the separation of charge in the
adjacent C—H bond so that the C would have a partial negative charge and the H would have a partial
positive charge. This would make the H more likely to be donated to a hydrogen bond acceptor group.
3. Rank the water solubility of the following compounds:

(a) H3C—CH2—O—CH3
(b)

(c)

(d) H3C—CH2—CH3
(e)

Answer:

From most soluble (most polar) to least soluble (least polar): c, b, e, a, d.

4. Where would the following substances partition in water containing palmitic acid micelles? (a)
+
H3N—CH2—COO–, (b) +H3N—(CH2)11—COO–, (c) H3C—(CH2)11—COO–

Answer:

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(a) Water;
(b) water;
(c) micelle.
5. Explain why water forms nearly spherical droplets on the surface of a freshly waxed car. Why doesn't
water bead on a clean windshield?

Answer:

The waxed car is a hydrophobic surface. To minimize its interaction with the hydrophobic molecules
(wax), each water drop minimizes its surface area by becoming a sphere (the geometrical shape with the
lowest possible ratio of surface to volume). Water does not bead on glass, because the glass presents a
hydrophilic surface with which the water molecules can interact. This allows the water to spread out.
6. Describe what happens when a dialysis bag containing pure water is suspended in a beaker of seawater.
What would happen if the dialysis membrane were permeable to water but not solutes?

Answer:

Water molecules move from inside the dialysis bag to the surrounding seawater by osmosis. Ions from the
seawater diffuse into the dialysis bag. At equilibrium, the compositions of the solutions inside and outside
the dialysis bag are identical. If the membrane were solute-impermeable, essentially all the water would
leave the dialysis bag.
7. Draw the structures of the conjugate bases of the following acids:

Answer:

8. Indicate the ionic species that predominates at pH 4, 8, and 11 for (a) ammonia and (b) phosphoric acid.

Answer:

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(a) pH 4, ; pH 8, ; pH 11, NH3.

(b) pH 4, ; pH 8, ; pH 11, .

9. Calculate the pH of a 200 mL solution of pure water to which has been added 50 mL of 1 mM HCl.

Answer:

The increase in [H+] due to the addition of HCl is (50 mL) (l mM)/(250 mL) = 0.2 mM = 2 × 10–4 M.
Because the [H+] of pure water, 10–7 M, is relatively insignificant, the pH of the solution is equal to
–log(2 × 10–4) or 3.7.
10. Calculate the pH of a 1 L solution containing (a) 10 mL of 5 M NaOH, (b) 10 mL of 100 mM glycine and
20 mL of 5 M HCl, and (c) 10 mL of 2 M acetic acid and 5 g of sodium acetate (formula weight 82 g ·
mol–1).

Answer:

(a) (0.010 L)(5 mol · L–1 NaOH)/(1 L) = 0.05 M NaOH = 0.05 M OH–

[H+] = Kw/[OH–] = (10–14)/(0.05) = 2 × 10–13 M

pH = –log [H+] = –log (2 × 10–13) = 12.7

(b) (0.020 L)(5 mol · L–1 HCl)/(1 L) = 0.1 M HCl ≡ 0.1 M H+

Since the contribution of 0.01 L × 100 mM/(1 L) = 1 mM glycine is insignificant in the presence
of 0.1 M HCl, pH = –log [H+] = –log (0.1) = 1.0
(c) pH = pK + log ([acetate]/[acetic acid])

[acetate] = (5 g)(1 mol/82 g)/(1 L) = 0.061 M

[acetic acid] = (0.01 L)(2 mol · L–1)/(1 L) = 0.02 M

pH = 4.76 + log (0.061/0.02) = 4.76 + 0.48 = 5.24

11. Calculate the standard free energy change for the dissociation of HEPES.

Answer:

The standard free energy change can be calculated using Eq. 1-16 and the value of K from Table 2-4.

12. A solution is made by mixing 50 mL of 2.0 M K2HPO4 and 25 mL of 2.0 M KH2PO4. The solution is
diluted to a final volume of 200 mL. What is the pH of the final solution?

Answer:

The pK corresponding to the equilibrium between (HA) and (A–) is 6.82 (Table 2-4).

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The concentration of A– is (50 mL)(2.0 M)/(200 mL) = 0.5 M, and the concentration of HA is (25
mL)(2.0 M)/(200 mL) = 0.25 M. Substitute these values into the Henderson–Hasselbalch equation (Eq.
2-9):

13. What is the pK of the weak acid HA if a solution containing 0.1 M HA and 0.2 M A– has a pH of 6.5?

Answer:

Use the Henderson–Hasselbalch equation (Eq. 2-9) and solve for pK:

14. How many grams of sodium succinate (formula weight 140 g · mol–1) and disodium succinate (formula
weight 162 g · mol–1) must be added to 1 L of water to produce a solution with pH 6.0 and a total solute
concentration of 50 mM?

Answer:

Let HA = sodium succinate and A– = disodium succinate.

[A–] + [HA] = 0.05 M, so [A–] = 0.05 M – [HA]
From Eq. 2-9 and Table 2-4,
log ([A]/[HA]) = pH – pK = 6.0 – 5.64 = 0.36
[A–]/[HA] = antilog 0.36 = 2.29
(0.050 M – [HA])/[HA] = 2.29
[HA] = 0.015 M
[A–] = 0.050 M – 0.015 M = 0.035 M
grams of sodium succinate = (0.015 mol · L–1)(140 g · mol–1) × (1 L) = 2.1 g
grams of disodium succinate = (0.035 mol · L–1)(162 g · mol–1) × (1 L) = 5.7 g
15. Estimate the volume of a solution of 5 M NaOH that must be added to adjust the pH from 4 to 9 in 100
mL of a 100 mM solution of phosphoric acid.

Answer:

At pH 4, essentially all the phosphoric acid is in the form, and at pH 9, essentially all is in the

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form (Fig. 2-18). Therefore, the concentration of OH– required is equivalent to the
concentration of the acid: (0.100 mol · L–1 phosphoric acid)(0.1 L) = 0.01 mol NaOH required = (0.01
mol)(1 L/5 mol NaOH) = 0.002 L = 2 mL.
16.
(a) Would phosphoric acid or succinic acid be a better buffer at pH 5?
(b) Would ammonia or piperidine be a better buffer at pH 9?
(c) Would HEPES or Tris be a better buffer at pH 7.5?

Answer:

(a) Succinic acid;

(b) ammonia;
(c) HEPES.
17. You need a buffer at pH 7.5 for use in purifying a protein at 4°C. You have chosen Tris, pK 8.08, ΔH° =
50 kJ · mol–1. You carefully make up 0.01 M Tris buffer, pH 7.5 at 25°C, and store it in the cold box to
equilibrate it to the temperature of the purification. When you measure the pH of the temperature-
equilibrated buffer it has increased to 8.1. What is the explanation for this increase? How can you avoid
this problem?

Answer:

The dissociation of TrisH+ to its basic form and H+ is associated with a large, positive enthalpy change.
Consequently, heat is taken up by the reactant on dissociation. When the temperature is lowered, there is
less heat available for this process, shifting the equilibrium constant toward the associated form (the
effect of temperature on the equilibrium constant of a reaction is given by Eq. 1-18). To avoid this
problem, the buffer should be prepared at the same temperature as its planned use.
18. Glycine hydrochloride (Cl–H3N+CH2COOH) is a diprotic acid that contains a carboxylic acid group and
an ammonium group and is therefore called an amino acid. It is often used in biochemical buffers.

(a) Which proton would you expect to dissociate at a lower pH, the proton of the carboxylic acid
group or the ammonium group?
(b) Write the chemical equations describing the dissociation of the first and second protons of
Cl–H3N+CH2COOH.
(c) A solution containing 0.01 M Cl–H3N+CH2COOH and 0.02 M of the monodissociated species
has pH = 2.65. What is the pK of this dissociation?
(d) In analogy with Figure 2-18, sketch the titration curve of this diprotic acid.

Answer:

(a) Carboxylic acid groups are stronger acids than ammonium groups and therefore lose their protons
at lower pH values. This can be seen in Fig. 2-17, where the carboxylic acid group of CH3COOH
is 50% dissociated to CH3COO– + H+ at pH 4.7 while it is not until pH 9.25 that the ammonium
ion is 50% dissociated to NH3.
(b)

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(c) The pK values of glycine's two ionizable groups are sufficiently different so that the Henderson–
Hasselbalch equation (Section 2-2B) adequately describes the behavior of the solution of the
diacid and the monodissociated species.

(d)

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