Академический Документы
Профессиональный Документы
Культура Документы
Buffer solutions
Buffer pH range
Buffer capacity
Change of pH
Calculations
http://www.wewwchemistry.com/2012/12/how-do-buffers-work.html
Chapters
15.2
Pages
572-578
Chapters
18.2
Pages
711-717
Buffer Solutions
!! Buffer solution (or buffer) is a solution that resist the change of pH
(upon dilution, addition of H+/OH-)
Buffer is a solution containing a mixture of a
weak acid and its conjugate base (CH3COOH + CH3COO-)
weak base and its conjugate acid (NH3 + NH4+)
Buffer is prepared by
mixing a weak acid with a salt of this acid and a strong base
(CH3COOH + CH3COONa)
mixing a weak base and a salt of this base and a strong acid
(NH3 + NH4Cl)
partial neutralization of a weak acid with strong base
(x CH3COOH + NaOH x CH3COONa + (1-x) CH3COOH + H2O
partial neutralization of a weak base with strong acid
(x NH3 + HCl x NH4Cl + (1-x) NH3 + H2O)
Example
Which of the following combinations will result in a buffer solution?
Example
Which of the following combinations will result in a buffer solution?
50 103 0.1 5mmol of acid AND 35 103 0.2 7mmol of base Cant base & salt
5mmol of salt AND 2mmol of base
also make a
buffer?
The pH of a buffer
7.2
CH 3COONa CH 3COO Na
CH 3COO H 2O
6.7
CH 3COOH OH
{SB1} Na cS
{SB 2} CH 3COO CH 3COOH cS cA
{EN } Na H CH 3COO OH
CH 3COO H
Ka
CH 3COOH
K w H OH
6.2
pH
5.7
5.2
4.7
1.E-09
H cS K a H cA K a K w H K a K w 0
3
1.E-07
1.E-05
cbuffer
1.E-03
cS
1
cA
1.E-01
1.E+01
cS H cA K a H 0
CH 3COO H
Ka
CH 3COOH
c
H K a A
c
S
pH pK a log
CH 3COOH K cA
H K a
a
cS
CH 3COO
cS
cA
Henderson-Hasselbalch equation
pH pK a log
cconj. base
cacid
pH pK a log
cS
cA
7.2
6.7
pH
6.2
5.7
5.2
4.7
1.E-09
1.E-07
1.E-05
1.E-03
1.E-01
cbuffer
Henderson-Hasselbalch equation
pH pK a log
cconj. base
cacid
1.E+01
7.2
6.7
pH
6.2
5.7
5.2
4.7
0.0
0.5
1.0
1.5
cbuffer
Henderson-Hasselbalch equation
pH pK a log
cconj. base
cacid
2.0
Mechanism of buffering
If acid is added to the buffer it reacts with the conjugate base
H 3O CH 3COO
CH3COOH
CH 3COOH H 2O
CH 3COOH cA x
CH 3COO cS x
CH3COO- CH3COOH
CH3COO- CH3COOH
H+
CH3COO-
CH 3COO H 2O
CH 3COOH cA y
CH 3COO cS y
CH3COOH CH3COO-
Adding H+ is equivalent to
withdrawing OHy = -x
OH-
CH3COOH
CH3COO-
Mechanism of buffering
pH pK a log
cS x
cA x
9
8
7
pH
6
5
4
3
2
1
OH- added
H+ added
Mechanism of buffering
pH pK a log
cS x
cA x
14
12
pH
10
8
6
4
2
0
OH- added
H+ added
The buffer capacity is the amount of acid or base that can be added to the buffer
before the pH begins to change rapidly.
Buffers have optimum capacity when cS 1
cA
The higher the concentrations (cS, cA) the higher the buffer capacity
8
7
buffer capacity
pH range
pH
4
3
2
OH- added
H+ added
5.5
cS/cA=1/1
cS/cA=1/2
5.0
pH
cS/cA=2/1
cS/cA=1/10
4.5
cS/cA=10/1
4.0
3.5
OH- added
H+ added
Example
Will the following combinations result in a buffer solution?
H cS K a H cA K a K w H K a K w 0
3
buffer
H cS K a H K w H K a K w 0
3
CH 3COOH OH
In principle, it is a buffer
but with a very narrow pH range
and a very low buffer capacity
Buffers prepared from a weak base and a corresponding salt (weak base+strong acid)
NH 3 H 2O
NH 4 OH
NH 4 OH
Kb
NH 3
NH 3 K cB
OH K b
b
cS
NH 4
pOH pK b log
cS
cB
Comparison
Henderson-Hasselbalch
CH 3COOH
CH 3COO H
CH 3COO
pH pK a log
CH 3COOH
Heylman
NH 3 H 2O
NH 4 H 3O
NH 4
pOH pK b log
NH 3
NH 4
14 pH 14 pK a log
NH 3
pH pK a log
Heylman Equation
conj. base
pH pK a log
conj. acid
NH 3
NH 4
Calculations
A buffer solution is prepared by dissolving 12g of formic acid and 23g of sodium formate
in 1L of solution. Calculate the pH of the buffer.
K a , HCOOH 1.7 104
M HCOOH 46g/mol
M HCOONa 68g/mol
mHCOOH 12
0.261mol
M HCOOH 46
23
0.338mol
68
n
0.261
c A HCOOH
0.261mol/L
V
1
n
0.338
cS HCOONa
0.338mol/L
V
1
c
pH pKa log S
cA
nHCOONa
pH 3.77 log
0.338
3.88
0.261
Calculations
Caculate the pH of a buffer solution from previous example upon addition of
a) 0.1mol HCl
b) 0.1mol NaOH.
H HCOO HCOOH
OH HCOOH HCOO +H 2O
decrease cS cS cSo x
increase cS cS cSo x
increase c A c A c Ao x
decrease c A c A c Ao x
pH pK a log
cS
cA
pH pK a log
cS
cA
cSo x
pH pK a log o
cA x
cSo x
pH pK a log o
cA x
0.338 0.1
pH 3.77 log
0.261 0.1
pH 3.60
pH 3.77 log
pH 4.20
0.338 0.1
0.261 0.1
Calculations
Calculate a capacity of a buffer from previous example for a pH range 3-4.6
pH pK a log
cS
cA
pH pK a log
cS
cA
cSo x
pH pK a log o
cA x
cSo x
pH pK a log o
cA x
0.338 x
0.261 x
0.338 x
0.83 log
0.261 x
0.338 x
100.83
0.261 x
0.338 x
6.761
0.261 x
6.761 0.261 x 0.338 x
0.338 x
0.261 x
0.338 x
0.77 log
0.261 x
0.338 x
100.77
0.261 x
0.338 x
0.17
0.261 x
0.17 0.261 x 0.338 x
1.427 7.761x
1.17 x 0.294
x 0.184mol OH
x 0.251mol H
3 3.77 log
Calculations
Calculate a capacity of a buffer from previous example for a pH range 3-4.6
pH pK a log
cS
cA
pH pK a log
cSo x
pH pK a log o
cA x
cSo x
pH pK a log o
cA x 6
0.338 x5
0.261 x4
0.338 x
0.83 log
3
0.261 x
0.338 x
100.83
2
0.261 x
0.338 x
1
6.761
0.261 x
-0.3
6.761 0.261 x 0.338 x
0.338 x
0.261 x
0.338 x
0.77 log
0.261 x
0.338 x
100.77
0.261 x
0.338 x
0.17
0.261 x
0.3
0.17 0.261 x 0.338 x
3 3.77 log
pH
cS
cA
-0.2
-0.1
0.1
H+ added / mol
0.2
1.427 7.761x
1.17 x 0.294
x 0.184mol OH
x 0.251mol H
pH pK a , H 2CO3
H 2CO3 (aq )
H 2O (l ) CO2 ( g )
HCO3
log
H 2CO3
pK a , H 2CO3 6.37
HgbH O2
HgbO2 H