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10
8
pH
6
4 2 0
Half-way Point
pKa
HCOOH
0.5
1.0
The titration curves of several weak acids. What 2 things do you notice?
Polyprotic acid
When an acid has more than 1 dissociable H+, dissociate in discrete steps; each proton of the weak acid has a distinct pKa Polyprotic acid an acid that has more than one dissociable proton; for example phosphoric acid (H3PO4) has 3 pKa and 3 equivalents of OH- are required for neutralization H3PO4 H+ + H2PO4pKa = 2.15
H2PO4HPO4-2
H+ + HPO4-2
H+ + PO4-3
pKa = 7.20**
pKa = 12.4
Sample Problem
If the total cellular concentration of phosphate is 20 mM in plasma at pH = 7.4. What is the distribution of the major phosphate species? pKa = pK2 = 7.2
Why pKa of 7.2?
pH = pKa + log [HPO4-2] or 7.4 = 7.2 + log [HPO4-2] [H2PO4-] [H2PO4-] 0.2 = log [HPO4-2] = 100.2 = [HPO4-2] =1.58 What does this tell you? [H2PO4-] [H2PO4-] Tells you ratio is 1.58 or 1.58/1 so total of 2.58 parts Know [HPO4-2] + [H2PO4-] = 20 mM (or 0.02 M) 1.58 + 1 = 20 mM What portion of 0.02 M or 20 mM is [HPO4-2] and [H2PO4-] ? 20 mM / 2.58 = 7.75 mM So [HPO4-2] = 12.25 mM and [H2PO4-] = 7.75 mM
What formula What does C tell can be used you? with B? What can be determined?
[A-]= HPO4-2 [HA]= H2PO4pH=7.4 pKa = 7.2 7.4=7.2 +log [HPO4-2] [H2PO4-] 0.2 = log [HPO4-2] [H2PO4-] Antilog x = 10x
Use HH equation
Good practice problems: end of chapter 2: 1a and 1b, 2a-d , and 3; Later 4-7 as we get to them
HA + H2O H3O+ + A- or can infer the water HA H+ + A- which infers a weak acid in water.
Situations where you add a strong acid/base to a weak acid/base OR add a salt solution to a weak acid/base. What then? Take it one step at a time!
1. Recall strong acids, bases, salts completely dissociate, so if have acetic acid (weak) and add sodium acetate (salt): then have HA H+ + A- (dont know how much without the pKa). Also have NaA Na+ + A-. So have 2 sources of A-. Must consider both: Must add [A-] from HA to the [A-] from NaAc. 2. Sometimes will have 2 sources of H+ (mixing a strong and weak acid). Again, must consider BOTH sources of H+ in your calculations: add [H+] from HA to the [H+] from strong acid.
HA HCl
H+ + AH+ + Cl-
Contd 3.
If adding a strong base requires special consideration. Must consider [OH- or A-] from the weak base and the strong base. The strong base will neutralize an equivalent number of mol of HA gives you a new starting [HA] AND yields an equivalent amount of A-. Why? HA NaOH H+ + ANa+ + OH-
4.
Remember to take one step at a time. Sometimes you will have to calculate several intermediate values before you can calculate what the problem is asking for.
Contd 5. NOTE: At any point during the titration of HA, the pH can be calculated using the Henderson-Hasselbalch Equation: pH = pKa + log [A-] / [HA] Example: After adding 100 ml of 0.1 M KOH to 500 ml of 0.1 M of weak acid (Ka = 1 x 10-5, pKa = 5), what is the pH? What we know: 0.1 L of 0.1 M KOH has been added to a weak acid. 0.1 M = 0.1 mol/L (0.1 L) = 0.01 mol, So 0.01 mol of OHneutralize 0.01 mol of HA and forms 0.01 M of A-. How many mol HA remains? How much did we start with?
Started with 0.1 M = 0.1 mol/L (0.5 L) = 0.05 mol of HA initially. Added 0.01 mol of OH- (neutralized 0.01 mol of HA). So have 0.05 0.01 = 0.04 mol HA left. Generated 0.01 mol A-
Continued:
The volume also has changed but NOT the ratio of mol A-/mol HA (mol is volume independent);
Use HH equation: pH= pKa + log [A-]/[HA] pH = 5.0 + log 0.01/0.04 = 5.0 + log 0.25 A- from HA can be ignored. Why?
Then have a new problem: The log of 0.25 is a negative number!! pH can NOT be a negative #. **To avoid dealing with the log of a negative number HendersonHasselbalch can be written as follows:
Change pH= pKa + log [A-]/[HA] to pH = pKa log [HA]/[A-] in the same way log x = log 1/x.
Gone From: pH= pKa + log [A-]/[HA] To: pH = pKa log [HA]/[A-]
So pH = 5 log 0.04/0.01 = 5 - log 4 = 5 - 0.602= 4.40 Can be seen in the Henderson-Hasselbach derivation (next slide). This is with 100 ml of 0.1 M KOH. If the problem reads: When 250 ml of 0.1 M KOH is added, then HA is 50% titrated. Why? What does this tell you? [HA] = 0.1 M = 0.1 mol/L (0.5 L) = 0.05 mol [KOH] = 0.1 mol/L (0.25 L) = 0.025 mol of OH- (neutralizes 50% of HA) Tells you [A-] = [HA] and log [A-]/[HA] = log 1 = 0 So pH = pKa.
Derivation of Henderson-Hasselbalch
Start with Ka = [H+][A-] / [HA] Rearrange the expression by (a) inverting each side and (b) multiply by Ka and [H+] : 1/Ka = [HA]/ [H+] [A-] Ka[H+] (1/Ka) = Ka [H+] ([HA]/ [H+][A-])=(Ka [H+]) [HA]/ [H+] [A-]) Gives you: [H+] = Ka ([HA]/[A-]) Take the -log of each side: -log [H+] = -log Ka log[HA]/[A-] Which is pH = pKa log[HA]/[A-] Or pH = pKa + log [A-]/[HA]
Buffers - Properties
5. Buffers can only be used reliably within one pH unit of their pKa. Why? At ph>1 from the pKa, the concentration of one of the buffer components is too low to absorb the influx of H+ and OH6. Molarity of a buffer is defined as the SUM of the concentrations of the acid and conjugate base forms. 7. Cellular buffers must have a pKa near 7 AND compatible with the metabolism of the cell; intracellular and extracellular fluids must maintain a relatively constant pH. Intracellular buffers: Extracellular fluid: *phosphate system (HPO4-2 / H2PO4-) histidine system; pH range 6.9-7.4 bicarbonate/carbonic acid system (HCO3- / H2CO3) Blood is maintained at pH 7.4; Closely connected to metabolism, lung and kidney function.
Buffer Problem. What are the concentrations of HA and A- in a 0.2 M acetate buffer, pH=5 ? (acetic acid pKa = 4.77, Ka = 1.7 x 10-5) Buffer means has acid and conjugate base.
NOTE: Can calculate 2 ways: using Ka or Henderson Hasselbalch. Using Ka: Ka = [H+][A-]/[HA] Using HH: still x = [A-]; [HA] = 0.2 x 1.7 X 10-5 = [H+][A-] /[HA] 5 = 4.77 + log (x) / 0.2-x x = [A-]; [H+]=10-5; [HA] = 0.2 x; 0.23 = log (x) / 0.2 - x 1.7 X 10-5 = (10-5)(x) / 0.2 x antilog 0.23 = x/0.2-x 1.7 X 10-5 (0.2-x) = 1 X 10-5x 1.7 = x / 0.2-x 3.4 X 10-6 1.7 X 10-5x = 1 X10-5x 1.7 (0.2 x) = x 3.4 X 10-6 = 2.7 X 10-5 x 0.34 1.7x =x x = 3.4 X 10-6 / 2.7 X 10-5 0.34 = 2.7 x x = 0.126 M = [A-] x = 0.34/2.7 or x = 0.126 M A0.2 -0.126 = 0.074 M HA 0.2 0.126 = 0.074 M HA