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Slide 1
Slide 2
Slide 3
Review of Logarithmic
Calculations
What is pH if [H+ ] is 3.2 x 10-4 M?
log 3.2 x 10 -4 = log3.2 + log10 4
= 0.51(the mantissa) 4(the characteristic)
= -3.49
so pH = -(-3.49) = 3.49
What is [H +] if pH is 8.56?
[H + ] =10 pH =10 8.56 =100.44 x 10 9
= 2.75 x 10 9
Lecture 3, page 1
Slide 4
Need Review in such
calculations?
Visit the pH drill web site
Visit your textbook web site
Slide 6
or
HA
H+ + A -
[ H+] [ A- ]
Ka =
[HA]
Lecture 3, page 2
Slide 7 Try the formula (Kac)1/2 first to see if x
Calculation of [H+] for a is small enough relative to c to ignore.
If not, then you need to use the
Weak Acid ([HA]=c) quadratic equation. Note we are
HA
H+ + A -
assuming that [H+] = [A-], when
c-x x x actually [H+]=[A-]+[OH-]. But if the
Ka =
x2 solution is acidic, [H+]>>[OH-] and the
(c x)
hydroxide term can be ignored. That
x2
if x < 0.05c, K a = and x = K ac might not be the case for very dilute
c
i f x 0.05c, x + Ka x + K ac = 0
2 solutions, or for Kas approaching 7
and above. For Kas above 7, the
Ka K a 4K ac
2
Take logarithm:
[HA]
log[H + ] = logK a + log
[A ]
[HA]
log[H + ] = logK a log
[A ]
[A ]
pH = pK + log
[HA]
Slide 9
A Base Can Be Treated As an
Acid
BH+ + OH
B + H2 O
[BH+ ][OH ] [BH+ ][OH ]
Kb = =
[B][HO]
2 [B]
B + H+
can also be written as: BH +
+
[B][H ]
Ka =
[BH + ]
[B][H+ ] [BH + ][OH ]
and K a x K b = x = [H + ][OH ] = K w
[BH+ ] [B]
Lecture 3, page 3
Slide
10 Difference in an Acid and a
Base Dissociation
HA H+ + A-
Charge separation; dielectric constant affects Ka
BH+ H+ + B
No charge separation; no dielectric constant
affect on Ka
HA + OH-
A- + H 2O
before 10 mmol x mmol small
after (10-x) mmol small x mmol
[ A ] x mmol/volume
and pH = pK a + log = pK a + log
[HA] (10-x) mmol/volume
Slide
12 Distinguish Between Fraction of
Base Form and Ratio of Base/Acid
HA A- A -/HA A -/(HA+A-)
Lecture 3, page 4
Slide Rough rule of thumb:
13 1% titration, pH = pK-2
Sketching Titration Curves 10% titration, pH = pK-1
50% titration, pH = pK
According to ratio of A -/HA 90% titration, pH=pK+1
Fraction Ratio Log(ratio) pH
99% titration, pH=pK+2
0.10 0.11 -0.96 pKa-0.96
0.25 0.33 -0.48 pKa-0.48
These calculations assume that [A-
0.50 1.0 0.0 pKa
]=concentration of hydroxide added.
0.75 3.0 0.48 pKa+0.48 That is not necessarily the case for
0.90 9.0 0.95 pKa+0.95 acids with very low pKs, because you
also have to take into account the A-
formed in the dissociation of the acid
before you started adding base.
Slide
14 Sketching Titration Curves
(cont)
The shape of all curves are the same
The position of the curves varies with pKa
See Figure 2.13
Curves for diprotic and triprotic acids can
be laid from end to end
See Figure 2.14
Slide
15
Buffers
A weak acid and its conjugate base
constitute a buffer
Buffers resist change in pH
Buffers are most effective at the pk of the
weak acid
Buffer capacity depends on concentration
Refer to Figure 2.15
See Textbook website discussion of buffers
Lecture 3, page 5
Slide
16
Phosphate Buffer
Best buffer at its pKs; pK 2 most
physiologically relevant
pK1 =2.15, pK2=7.20, pK3=12.40
As a take-home exercise, calculate the
concentration of all ionic species of
phosphate ([H3 PO4], [H 2PO4 -], [HPO4 2-],
and [PO43-]) in 0.01 M total phosphate at pH
7.4 (the pH of blood).
Slide
17
Hint for Phosphate Calculation
You have three equilibrium equations
For K1 , K2, and K3
You have one conservation equation
[H3PO4]+[H 2PO4-]+[HPO42-]+[PO4 3-]=0.01 M
Four equations and four unknowns can be
solved by simultaneous equations. There
are several algebraic ways to proceed.
Slide
18
Bicarbonate Buffer
A major buffer in blood
Also in equilibrium with gaseous CO2
Relevant equations:
CO 2(d)
CO 2(g)
H 2 CO3
CO 2(d) + H 2 O
H + + HCO3
H 2 CO3
Lecture 3, page 6
Slide While a normal titration is plotting the
19 curve for pH=pK+log(x/c-x), when
Bicarbonate Buffer, (cont) carbonic acid is titrated the
concentration of the acid does not
The pK1 recorded for bicarbonate depends decrease because it is replenished by
on whether you are referring to [H2CO3 ] the gaseous CO2 in equilibrium with
alone, or total dissolved CO2 which is the solution. So the equation becomes
[H2 CO3 ] + [CO2(d) ] ([CO2 ]/[H2 CO3 ] = 500
pH=pK+log(x/c), and this curve does
[HCO3 ]
pH = pK1 + log , then pK1 = 3.57 not turn up, but keeps getting flatter.
[H2 CO3 ]
Hence bicarbonate is a better buffer at
[HCO3 ]
pH = pK1(overall) + log 7.4 than at 6.1, even though that is
[H2 CO3 + CO2 ( d ) ]
then pK1(overall) = 6.1
more than one pH unit above the pK
Slide
20
Laboratory Buffers
Most laboratory experiments require the use
of buffers to control the pH. Phosphate
buffer is often used, but a number of other
buffers referred to as the Good buffers
(after N.E.Good) have been developed for
experimental use.
Lecture 3, page 7