Entry Task: Feb 12

th
Tuesday
Define Buffer capacity


You have 5 minutes
Agenda
Discuss Buffer ws 1
In-class notes little more buffer info and
practice on Titrations

HW: Buffers ws #2
Explain why a mixture of HCl and KCl does not
function as a buffer, whereas a mixture of
HC
2
H
3
O
2
and NaC
2
H
3
O
2
does?
HCl and KCl are conjugate-pairs, problem is that
potassium is an alkali metal and will stay
dissociated and add more + to the system
making it more acidic.


2. What factors determine a) the pH, and b) the
buffer capacity of a buffer solution?
A) The pH of a buffer is determined by Ka for
the conjugate acid present and the ratio of
the conjugate base concentration to the
conjugate acid concentration.
B) The buffering capacity of buffer is
determined by the concentrations of the
conjugate acid and conjugate base present.
Higher the concentration the higher the
capacity.
3. In a solution, when the concentrations of a weak
acid and its conjugate base are equal,
A) the system is not at equilibrium.
B) the buffering capacity is significantly decreased.
C) the -log of the [H+] and the -log of the Ka are equal.
D) all of the above are true.

4. Of the following solutions, which has the greatest
buffering capacity?
A) 0.821 M HF and 0.217 M NaF
B) 0.821 M HF and 0.909 M NaF
C) 0.100 M HF and 0.217 M NaF
D) 0.121 M HF and 0.667 M NaF
E) They are all buffer solutions and would all have the
same capacity.

5. The addition of hydrofluoric acid and __________
to water produces a buffer solution.
A) HCl
B) NaNO3
C) NaCl
D) NaOH
E) NaBr

6. Which of the following could be added to a solution
of sodium acetate to produce a buffer?
A) acetic acid only
B) acetic acid or hydrochloric acid
C) hydrochloric acid only
D) potassium acetate only
E) sodium chloride or potassium acetate

7. A solution is prepared by dissolving 0.23 mol of
hydrazoic acid and 0.27 mol of sodium azide in water
sufficient to yield 1.00 L of solution. The addition of 0.05
mol of NaOH to this buffer solution causes the pH to
increase slightly. The pH does not increase drastically
because the NaOH reacts with the __________ present in
the buffer solution. The K
a
of hydrazoic acid is 1.9 10
-5
.
A) H
2
O
B) H
3
O+
C) azide
D) hydrazoic acid
E) This is a buffer solution: the pH does not change upon
addition of acid or base.

8. What is the pH of a buffer solution that is 0.211 M
in lactic acid and 0.111 M in sodium lactate? The Ka of
lactic acid is 1.4 10
-4
.
Ka = [x][0.111]
[0.211]
1.4 x 10
-4
= [x][0.111]
[0.211]
Rearrange to
get X by itself
x= (1.4 x 10
-4
)(0.211)
0.111
x = [H+]= 2.66 x 10
-4

pH = -log(2.66 x 10
-4
) = 3.57
Things we have not considered
*volume changes
*grams mole Molarity
*effect on pH
*addition of acid/base and change
in equilibrium
Buffer Problems
Hurdles-
1
st -
Which species in problem is acid or base?
2
nd
Kb value for OH
-
or Ka for H
+
3
rd
Setting up Ka or Kb expression correctly (1
st
)
4
th
Is there any changes in concentrations from given:
*Grams Moles Molarity
*Mixing two different volumes (M
1
V
1
= M
2
V
2
)
*Addition of a new species (ICE table)

Different Volumes

Treat as dilution problems
1a. Calculate the pH of a buffer that is 0.100 M in NaHCO
3

and 0.125M in Na
2
CO
3
. b. Calculate the pH of a solution
formed by mixing 55mls of 0.20M NaHCO
3
with 65mls of 0.15
M Na
2
CO
3
.
Ka = [H+][CO
3
-2
]
[HCO
3
-
]
5.6 x 10
-11
= [x][0.125]
[0.100]
Who is the conjugate in this reaction?
x= (5.6 x 10
-11
)(0.100)
0.125
x = [H+]= 4.48 x 10
-11

pH = -log(4.48 x 10
-11
) = 10.35
HCO
3
-
so we use H
2
CO
3
Ka value= 5.6x10
-11
Provide the Ka expression
Provide the Ka express with #
Rearrange to get X by itself
1a. Calculate the pH of a buffer that is 0.100 M in NaHCO
3

and 0.125M in Na
2
CO
3
. b. Calculate the pH of a solution
formed by mixing 55mls of 0.20M NaHCO
3
with 65mls of 0.15
M Na
2
CO
3
.
Ka = [H+][CO
3
-2
]
[HCO
3
-
]
5.6 x 10
-11
= [x][0.125]
[0.100]
OR use the H-H equation
pH = pK
a
+ log
[base]
[acid]
pH = 10.25 + log
[0.125]
[0.100]
pH = 10.25 + 0.0969
10.35 = 10.25 + 0.0969
1a. Calculate the pH of a buffer that is 0.100 M in NaHCO
3

and 0.125M in Na
2
CO
3
. b. Calculate the pH of a solution
formed by mixing 55mls of 0.20M NaHCO
3
with 65mls of
0.15 M Na
2
CO
3
.
NOTICE we have different volumes!!
What will be the TOTAL VOLUME?

120 mls
We have diluted our mixture so we set up a dilution
problem- MAKE SURE volume units are the same!!
M
1
V
1
= M
2
V
2
(0.20M)(0.055L) = (x) (0.120L)=

(0.15M)(0.065L) = (x)(0.120L) =
9.17x10
-2
M of NaHCO
3

(new M)
8.125x10
-2
Mof Na
2
CO
3 (new M)

x= (5.6 x 10
-11
)(9.17x10
-2
)
8.125x10
-2

x = [H+]= 6.32 x 10
-11

pH = -log(6.32 x 10
-11
) = 10.20
1a. Calculate the pH of a buffer that is 0.100 M in NaHCO
3

and 0.125M in Na
2
CO
3
. b. Calculate the pH of a solution
formed by mixing 55mls of 0.20M NaHCO
3
with 65mls of
0.15 M Na
2
CO
3
.
5.6 x 10
-11
= [x][8.125x10
-2
]
[9.17x10
-2
]
NOTICE we have different volumes!!
What will be the TOTAL VOLUME?

120 mls
H-H equation
pH = 10.25 + log
[8.125 x10
-2
]
[9.17x10
-2

10.20 = 10.25 + -0.0525
2a. Calculate the pH of a buffer that is 0.12 M in lactic acid
and 0.11M in sodium lactate. b. Calculate the pH of a
solution formed by mixing 85mls of 0.13M lactic acid with
95mls of 0.15M sodium lactate. Ka= 1.4 10
-4

1.4 x 10
-4
= [x][0.11]
[0.12]
pH = pK
a
+ log
[base]
[acid]
pH = 3.85 + log
[0.11]
[0.12]
3.8 = 3.85 + -0.0378
2a Calculate the pH of a buffer that is 0.12 M in lactic acid and
0.11M in sodium lactate. B. Calculate the pH of a solution
formed by mixing 85mls of 0.13M lactic acid with 95mls of
0.15M sodium lactate.
What will be the TOTAL VOLUME?

180 mls
We have diluted our mixture so we set up a dilution
problem- MAKE SURE volume units are the same!!
(0.13M)(0.085L) = (x)(0.180L) = 6.14x10
-2
M of lactic acid
(new M)
(0.15M)(0.095L) = (x)(0.180L)= 7.92x10
-2
M of sodium lactate


(new M)

pH = 3.85 + log
[7.92 x10
-2
]
[6.14x10
-2
]
3.96 = 3.85 + 0.011
Addition of strong acid-base
Addition of strong acid
NaHCO
3
+ HCl H+ + CO
3
-2

NaHCO
3

H
+


CO
3
-2


Before 0.100 mol 0.010
mol
0.125 mol
Change +0.010
mol
-0.010 -0.010
mol
After Reaction 0.110 mol 0.000
mol
0.115 mol
Using the same information given in 1a calculate the pH after
the addition of 0.010M of HCl.
Added neutralizes any CO
3
-2
ions
Calculating pH Changes in Buffers
Ka expression with NEW molarities to calculate new pH
Ka = [H+][CO
3
-2
]
[HCO
3
-
]
5.6 x 10
-11
= [x][0.115]
[0.110]
x= (5.6 x 10
-11
)(0.110)
0.115
x = [H+]= 5.83 x 10
-11

pH = -log(3.97 x 10
-11
) = 10.3
Rearrange to get X by itself
Calculating pH Changes in Buffers
Using the same information given in 1a calculate the pH after the
addition of 0.050M of NaOH
NaHCO
3
OH

CO
2
2


Before 0.100 mol 0.050
mol
0.125
mol
Change -0.050
mol
-0.050 +0.050
mol
After Reaction 0.050 mol 0.000
mol
0.175
mol
Added
neutralizes
any H+ ions
Calculating pH Changes in Buffers
Ka expression with NEW molarities to calculate new pH
Ka = [H+][CO
3
-2
]
[HCO
3
-
]
5.6 x 10
-11
= [x][0.175]
[0.050]
x= (5.6 x 10
-11
)(0.050)
0.175
x = [H+]= 1.6 x 10
-11

pH = -log(1.6 x 10
-11
) = 10.8
Rearrange to get X by itself
Titration:
A laboratory method for determining the
concentration of an unknown acid or base
using a neutralization reaction.

A standard solution,(a solution of known
concentration-titrant), is used.

Titration
A known concentration of base
(or acid) is slowly added to a
solution of acid (or base).

After titration- we have a known
volume and concentration from
titrant
(M
1
)(V
1
). The unknown has a
known volume(V
2
) so we can
calculate (M
2
).

(M
1
)(V
1
)= (M
2
)(V
2
)

Titrant-known of
concentration
Unknown
concentration with a
known volume
Titration
A pH meter or indicators
are used to determine
when the solution has
reached the equivalence
point, at which the
stoichiometric amount of
acid equals that of base.
pH Titration Curve
pH titration curve, a
graph of pH as a
function of volume
of the added titrant.
The pH curve can:
*help determine
equivalence point
*determine the pH
indicators needed for
Ka or Kb determination.
pH Titration Curve
Can you identify the
titrant?
Is it an acid or base.
Base
*pH is increasing
*it levels off with lots of
base.
Strong Acid- Strong Base Titration
4 regions of a titration curve
1
st
- Initial pH-
its really low- probably
a strong acid.
2
nd
- Between initial
and equivalence pt.
rises slowly then rapidly
around the ~SAME~
volume as the
unknown.
Strong Acid- Strong Base Titration
4 regions of a titration curve
3
rd
Equivalence pt
[H+] = [OH-] = pH 7
4
th
After equivalence
pt.
Has plateaued with
excess base
Titration of a Strong Acid with a
Strong Base
From the start of
the titration to near
the equivalence
point, the pH goes
up slowly.
Titration of a Strong Acid with a
Strong Base
Just before and
after the
equivalence point,
the pH increases
rapidly.

Titration of a Strong Acid with a
Strong Base
At the equivalence
point, moles acid =
moles base, and the
solution contains
only water and the
salt from the cation
of the base and the
anion of the acid.

Titration of a Strong Acid with a
Strong Base
As more base is
added, the increase in
pH again levels off.
We will learn how to CALCULATE the
equivalence point later.
Titration of a Weak Acid with a
Strong Base
Which way will the equilibrium shift in the case
of weak acid and strong base?
Titration of a Weak Acid with a Strong Base
1
st
- Initial pH-
~3 or 4 is a stronger weak
acid
2
nd
- Between initial and
equivalence pt.
2 things to consider
1. neutralization of weak
acid by strong base
2. Strong base acts as a
buffer so it resists the
titration
pH of your weak acid is the
amount for neutralization of
base- of 50 mls (25 mls)
and pH of ~4.8
Titration of a Weak Acid with a Strong Base
3
rd
At equivalence pt
~The pH here is above 7
which is what we
expected
4
th
After equivalence pt
The curve looks very
similar to a strong
acid/strong base curve.
Titration of a Weak Base with a
Strong Acid
Which way will the equilibrium shift in the case of weak base
and strong acid?
Titration of a Weak base with a Strong acid
1
st
- Initial pH-
its really high probably a
strong base.
2
nd
- Between initial and
equivalence pt.
2 things to consider
1. neutralization of weak
base by strong acid
2. Strong acid acts as a
buffer so it resists the
titration
Strong base
Titration of a Weak base with a Strong acid
3
rd
At equivalence pt
~The pH here below 7
which is what we
expected
4
th
After equivalence pt
The curve looks very
similar to a strong
acid/strong base
curve.
Strong base
Titration of a Weak Acid with a Strong Base
With weaker acids,
the initial pH is higher
and pH changes near
the equivalence point
are more subtle.
Titrations of Polyprotic Acids
In these cases there is
an equivalence point
for each dissociation.