CHM 116 Spring 2012

Lecture 14
Section 19.1

Next Lecture
Read Sec. 19.2 In Silberberg

Lab: Acid-Base Equilibria Part I

Understand:
Acid-base titrations equivalence point, half-equivalence point, pKa and Ka, conjugate acids and bases Colorimetric vs. pH titration Dilution factor Volumetric measurements Use of pH electrodes with LabView

Lab: Acid-Base Equilibria Part I

Step 1: Determine [NaOH] in an unknown solution by titration with HCl of known concentration.

For each step, youll do 3 titrations: 1 scout colorimetric, 1 careful colorimetric, and 1 pH (potentiometric) using LabView. NaOH of unknown concentration

HCl of known concentration + indicator

Step 2: determine [acetic acid] in diluted vinegar by titration with NaOH.

Buffers
What is a buffer:

Buffers generally consist of:

Buffers
The pH of our blood is about 7.4 . If it rises above about 7.8 or falls below 6.8 irreversible brain damage and death can occur. Buffer: H2CO3/HCO3This is a special system. The concentration of CO2 in the lung has a direct impact on the pH of the blood. CO2 + H2O H3O+ + HCO3-

Common Ion Effect

The ionization of a weak electrolyte in a solution decreases significantly when a salt of the weak electrolyte is added to the solution. This effect is called the common ion effect For example, the ionization of acetic acid in a solution will decrease when sodium acetate, NaCH3CO2 , or another acetate salt, is added to the solution. CH3CO2H + H2O

H3O+ + CH3CO2

The common ion effect can be explained sign le chateliers principle. The addition of the common ion shifts the equilibrium.

Buffers
A buffer is a mixture of roughly equal amounts of a weak conjugate acid/base pair in equilibrium. Buffer: HF/NaF Equilibrium: HF + H2O H3O+ + FAdd acid: [H3O+] increases & equilibrium shifts left to remove most of the H3O+ added HF + H2O H3O+ + FAdd base: [H3O+] decreases & equilibrium shifts right to restore most of the H3O+ removed HF + H2O H3O+ + FIn contrast, if we add acid or base to H2O, it stays as H3O+ (or OH-) and the pH changes more dramatically

Buffers
Buffer after addition of H3O+ Buffer with equal concentrations of conjugate base and acid Buffer after addition of OH-

H3O+

OH-

H2O + CH3COOH

H3O+ + CH3COO-

CH3COOH + OH-

H2O + CH3COO-

Note: no net increase in [H3O+]

Note: no net increase in [OH-]

Henderson-Hasselbalch equation simplifies calculations of pH of a buffered solution

HA + H2O H3O+ + ADoccam

Ka= [h3O +] [A-]/[HA] Log ka=log[h3o} + log [a]/[HA] -log [h3o] = - log Ka + log [A]/[HA] pH = pKa + log [A]/[HA]

Henderson-Hasselbalch equation simplifies calculations of pH of a buffered solution

HA + H2O H3O+ + A[A-] [HA]

pH = pKa + log

If [A-] = [HA] I. Log 1=0 II.

then pH = pKa

Buffers
What is the pH of a buffer that has [HOAc] = 0.700 M and [OAc-] = 0.600 M? HOAc + H2O OAc- + H3O+ Ka = 1.8 x 10-5 (pKa = 4.74)
Use equilibrium expression
[H3O+ ](0.600) Ka = 1.8 x 10 = 0.700
-5

or use HendersonHasselbalch equation

[H3O+] = 2.1 x 10-5 and pH = 4.68

pH = 4.74 + log = 4.74 - 0.06 pH = 4.68

0.600 0.700

How Do Buffers Work?

What is pH change when you add base to a buffer? Add 0.001 mole of NaOH(s) to 1 L of a HF / F- buffer Assume no V and all of added base converts HF to FDoccam

How Do Buffers Work?

What is pH change when you add base to a buffer? Add 0.001 mole of NaOH(s) to 1 L of a 1:1 HF / F- buffer Assume no V and all of added base converts HF to F-

pH changes from 3.17 to 3.18

0.001 mol NaOH in 1 L of pure water changes pH from 7 to 11

Buffer Capacity
Buffer solutions have a limited capacity to keep the pH relatively constant. The buffering will be overcome if so much acid or base is added that the ratio of the concentration of the weak acid or base and its salt changes too much. The more concentrated a buffer,

Buffer capacity is

Buffer Range
Buffer range is the pH range over which the buffer acts effectively.

1. If the ratio [A-]/[HA] is greater than 10 or less than 0.1, buffers are poor 2. If the concentration of one component is more than 10 times the other, the buffering action is poor.
pH = pKa + log10 (log 10 = 1) pH = pKa + 1 pH = pKa + log100 (log 100 = 2) pH = pKa + 2

Preparing a Buffer
1. Mix weak acid and its conjugate base. Pick an acid with a pKa approx. equal to the desired pH. 2. Start with a weak acid, and add a strong base to produce the conjugate base. (to half-way point of a titration)

3. Start with a weak base, and add a strong acid to produce the conjugate acid. (to half-way point of a titration)

Preparing a Buffer
Acidic buffer: Acetic acid / acetate ion

Mix CH3CO2H & NaCH3CO2 (CH3CO2 is the weak conjugate base) Add a little NaOH to CH3CO2H NaOH + CH3CO2H NaCH3CO2 + H2O

Add a little HCl to NaCH3CO2 HCl + NaCH3CO2 CH3CO2H + NaCl

Preparing a Buffer
Basic buffer: Ammonia / ammonium ion

Mix NH3 and NH4Cl (NH4+ is the weak conjugate acid) Add a little HCl to NH3 HCl + NH3 NH4+ + Cl-

Add a little NaOH to NH4Cl NaOH + NH4Cl NaCl + NH3

Buffers & Titration Curves

The math equations you will need: Equilibrium equation (for Ka , Kb , & Kw) For pH, pOH, & pK: pX = -log X X = [H3O+], X = 10-pX [OH-], or K

pKw = pH + pOH
Henderson-Hasselbalch equation: This equation relates pH, pKa, and the concentrations of a mixture of an acid and its conjugate base (a buffer).

The Role of Buffers in Blood

1. The pH of blood plasma is maintained at about 7.40 by several buffer systems, the most important is H2CO3 / HCO3- system.

2. As the H2CO3 / HCO3- concentrations change during buffering, the body can adjust the concentrations of either component by controlling the partial pressure of CO2 in your blood. Arterial blood contains around 40 mm Hg of CO2 gas.

Some Blood Equilibria

CO2(aq) + H2O (l) H2CO3 (aq) (catalyzed) (1) (2) (3) (4) H2CO3(aq) + H2O (l) H3O+ (aq) + HCO3- (aq) O2(aq) + HHb(aq) HHbO2 (aq) HHbO2 (aq) + H2O (l) H3O+ (aq) + HbO2 -(aq)

Doccam