Lecture 3 Notes---BCH 4053---Spring 2000

Slide 1

Definitions of pH and pOH

Because of large concentration range
(between about 10 M and 10-15 M) a
logarithmic scale of concentrations is
defined:
pH = -log[H +]
pOH = -log[OH-]

Slide 2

Relationship of pH and pOH

Since [H+][OH -] = 10 -14
-log[H+] + -log[OH-] = -log[10-14]
pH + pOH = 14
So pH = 14 pOH and pOH = 14 pH
Neutral solution, pH = pOH = 7
Acid solutions, [H+] > [OH-], pH < 7
Basic solutions, [H+] < [OH-], pH > 7
(See Table 2.2)

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 5 Other strong acids are HNO3 , HBr, HI,

Strong Acids versus Weak Acids
Strong acids completely dissociate
HCl H+ + Cl-
[H+] = [Cl -] + [OH-]
concentration will be given by HCl concentration
unless it is low enough that OH- cannot be
ignored.
Weak acids partly dissociate. The extent of
dissociation can be expressed by an equilibrium
constant, Ka
H2 SO4 (first proton dissociation),
HClO 3 , and HClO 4 . Note that a 10-9 M
solution of HCl would not have a pH
of 9! You could not ignore the
hydroxide concentration then, and
would need to solve the equation
[H+]=[Cl-]+Kw/[H+], where you
substitute Kw/[H+] for [OH-].

Slide 6

Weak Acid Dissociation

H 3O + + A-
HA + HO
2

acid base conjugate conjugate
acid base
[ H3 O+] [ A- ]
Ka =
[HA][HO] 2

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

and x = calculation should probably be done

2
using Kb.

Slide 8 Note there is a direct proportional

Henderson-Hasselbalch relationship between the hydrogen ion
concentration and the ratio of
Equation protonated forms. When [H+] = Ka,
Rearrange Ka expression: then [HA]/[A-] = 1.
[HA]
[H + ] = K a
[A ]

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

Slide Note that the ratio in the logarithm turn

11 Titration of a Weak Acid with a can be a ratio of quantity (moles) as
well as a ratio of concentrations,
Strong Base
because the volume is the same for
A strong base added to the equilibrium solution of the
weak acid will consume the H +, converting HA to A-. both the numerator and denominator.

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

This equation leads to the graph of Figure 2.12

Slide
12 Distinguish Between Fraction of
Base Form and Ratio of Base/Acid
HA A- A -/HA A -/(HA+A-)

90 mmol 10 mmol 10/90=0.11 10/100=0.10

75 mmol 25 mmol 25/75=0.33 25/100=0.25

50 mmol 50 mmol 50/50=1.0 50/100=0.50

25 mmol 75 mmol 75/25=3.0 75/100=0.75

10 mmol 90 mmol 90/10=9.0 90/100=0.90

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