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N.Mohamed 1
ACID-BASE
TITRATIONS
N.Mohamed 2
Titration
Titrationisisaatried-and-true
tried-and-truetechnique,
technique,capable
capableof
of
high
highprecision
precisionand andaccuracy.
accuracy.
N.Mohamed 3
N.Mohamed 4
before approximately .after endpoint
endpoint... at endpoint... (overshot)
N.Mohamed 5
Volumetric Analysis
Use 4 types of equilibria:
acid/base, precipitation,
complexometry, redox
TITRATION Amount of analyte in
a solution is determined from total
standard solution that had reacted
with it.
STANDARDISATION -
Determination of exact
concentration of a solution by
titrating with a primary standard.
N.Mohamed 6
Equivalence point - Titration
stage when no. of equivalents
of primary solution added is the
same as the analyte.
End-point - Titration stage
when there is a change in
colour of the indicator used.
Titration error - Difference
between end-point and
equivalent point.
PRIMARY STANDARDS
Compounds that had been used
directly or indirectly for the
preparation of standard
solution. Has high purity.
N.Mohamed 7
Primary standards
Requirements for a good primary
standard
High purity
Stable thermally, chemically
stable under normal lab
conditions.
High molecular mass reduce
errors in weighing
N.Mohamed 8
Criteria for a successful
titration
Reaction should:
have known stoichiometry e.g.,
HC2H3O2 + NaOH
NaC2H3O2 + H2O
Be complete, high K, no side-
rxn.
Be rapid.
Give a distinct change in
property of solution at end-point
(colour, pH, electrical properties,
etc). End-point can be easily
detected.
N.Mohamed 9
Neutralization titration
N.Mohamed 10
Acid-Base Titrations
Titration of Strong Acid + Strong
Base
50.0 mL 0.100 M HCl is titrated with 0.100
M NaOH. Calculate pH of solution after
adding 0.0, 25.0, 50.0 and 60.0 mL base.
Addition of 0.0 mL
pH = - log[H+] = - log (0.100)
= 1.00
Addition of 25.0 mL
HCl + NaOH NaCl + H2O
Initial, mmol 5.0 2.5 0 0
Equil, mmol 2.5 0 2.5 2.5
[H+] = 2.5 mmol = 0.033
(25.0 + 50.0) mL
pH = 1.48
N.Mohamed 11
Addition of 50.0 mL
N.Mohamed 12
Titration of Weak Acid +
Strong Base
50.0 mL of 0.100 M acetic acid is
titrated with 0.100 M NaOH.
Calculate the pH of the
solution after the addition of
0.0, 5.0, 50.0, 55.0 mL base.
N.Mohamed 13
Addition of 0.0 mL base
HOAc OAc- + H+
Initial, M 0.100 0 0
Equil, M 0.100-x x x
x.x = 1.75 x 10-5
0.100-x
Since CHOAc> 100Ka, x at the
denominator can be neglected.
x.x = 1.75 x 10-5
0.100
x = [H+] = 1.32 x 10-3 M
pH = 2.88
N.Mohamed 14
Addition of 5.0 mL NaOH
N.Mohamed 15
Addition of 50.0 mL NaOH
HOAc + NaOH NaOAc + H2O
Initial, mmol 5.00 5.00 0 0
Equil, 0 0 5.00 5.00
Equivalence point
[NaOAc] = 5.00 mmol
(50.0 + 50.0) mL
NaOAc OAc- + Na+
OAc- + H2O HOAc + OH-
Initial,M 0.05 0 0
Equil 0.050-x x x
Kb = Kw = 1.00 x 10-14 = x.x
Ka 1.75 x 10-5 0.05-x
Since CNaOAc > 100 Kb
1.00 x 10-14 = x.x = 5.71 x 10-10
1.75 x 10-5 0.05-x
x = [OH-] = 5.3 x 10-6 M
pOH = 5.28
N.Mohamed 16
pH = 14.00 5.28 = 8.72
Addition of 55.0 mL NaOH
N.Mohamed 17
For
Foraaweak
weakacid,
acid,we
westart
startwith
withionization
ionizationof
ofHA.
HA.
In
Inthe
thebuffer
bufferregion,
region,use
usethe
theHenderson-Hasselbalch
Henderson-Hasselbalchequation.
equation.
At -
Atthe
theequivalence
equivalencepoint,
point,AA-hydrolyzes
hydrolyzesas
asaaweak
weakbase.
base.
Beyond -
Beyondthe
theequivalence
equivalencepoint,
point,excess
excessOH
OH-dominates.
dominates.
AAweak
weakbase
baseisistreated
treatedsimilarly,
similarly,but
butbeginning
beginningwith
withbase
baseand
and
ending with acid.
ending with acid.
N.Mohamed 19
If colour of non-ionised formed is to
be seen,
[In-] = 1
[HIn] 10
pH = pKa + log (1/10)
If the colour of the ionised form is to
be seen,
[In-] = 10
[HIn]
pH = pKa + log (10)
Indicator range pH range for
colour changes
Thus indicator range is pH
pH = (pKa + 1) - (pKa - 1)
=2
N.Mohamed 21
pH
pHtransition
transitionrange
range==pKpKaa1.1.
We
Weselect
selectan
anindicator
indicatorwith
withaapK pKaanear
nearthe
the
equivalence point pH.
equivalence point pH.
Gary Christian,
Analytical
Chemistry, 6th
Ed. (Wiley)
Gary Christian,
Analytical
Chemistry, 6th
Ed. (Wiley)
N.Mohamed 23
0.001
M
0.01
M
0.1 M
Gary Christian,
Analytical
Chemistry, 6th
Ed. (Wiley)
N.Mohamed
Dependence of the magnitude of end-point break on 24
concentration.The concentrations of acid and titrant are
the same.
This
Thisisisthe
themirror
mirrorimage
imageof
ofthe
theHCl
HCl
titration curve.
titration curve.
Gary Christian,
Analytical
Chemistry, 6th
Ed. (Wiley)
N.Mohamed 25
Titration curve for 100 mL of 0.1 M NaOH versus 0.1 M HCl.
AAweak
weakacid
acidgives
givesaasmaller
smallerend
endpoint
pointbreak..
break.. AAstong
stongbase
base
titrant
titrantisisalways
alwaysused.
used.
We -
Westart
startwith
withHOAc.
HOAc. Then
Thenwe
wehave
haveaabuffer
buffermixture
mixtureofofOAc
OAc-and
and
HOAc.
HOAc.
At -
Atthe
theequivalence
equivalencepoint,
point,we
wehave
haveOAc
OAc,-,aaweak
weakbase.
base.
Beyond
Beyondthe
theequivalence
equivalencepoint,
point,we
wehave
haveexcess
excessNaOH
NaOH
(suppresses -
(suppressesOAcOAc-hydrolysis),
hydrolysis),and
andthe
thecurve
curvefollows
followsthat
thatfor
foraa
strong
strongacid
acidtitration.
titration.
Gary Christian,
Analytical
Chemistry, 6th
Ed. (Wiley)
N.Mohamed 26
Titration curve for 100 mL 0.1 M HOAc versus 0.1 M NaOH
The
Thebuffer
bufferregions
regionsare
areabout
aboutthe
thesame
samefor
forall
all
concentrations.
concentrations.
The
Theequivalence
equivalencepoint
pointpH
pHincreases
increaseswith
withincreasing
increasing
concentration.
concentration.
0.1
M
0.01 M
0.001 M
Gary Christian,
Analytical
Chemistry, 6th
Ed. (Wiley)
Gary Christian,
Analytical
Chemistry, 6th
Ed. (Wiley)
Titration curves for 100 N.Mohamed 28
mL 0.1 M weak acids of different
Ka values versus 0.1 M NaOH.
This
Thisisisthe
the
reverse
reverseof ofthe
the
HOAc titration
HOAc titration
curve.
curve.
We
Westart
startwith
with
NH
NH33 weakbase.
weak base.
Then
Thenwewehave
haveaa
buffer
buffermixture
mixtureofof
NH + and NH .
NH4 + and NH3 .
4 3
At
Atthe
the
equivalence
equivalence
point,
point,we
wehave
have
NH +, a weak
+
NH44 , a weak
acid.
acid.
Beyond
Beyondthe thee.p.,
e.p.,
we have excess
we have excess
HCl,
HCl,which
which
suppresses
suppressesthe the
hydrolysis
hydrolysis of of
NH +
NH44+, ,and
andthe
the
curve follows
curve follows
that
thatfor
foraastrong
strong
base
basetitration.
titration.
N.Mohamed 31
TITRATION OF
POLYPROTIC ACIDS
H+ will be neutralized, step
by step, starting with the
strongest H +, when a
polyprotic acid is titrated
with a strong base.
End point can be detected
when:
Ka1/Ka2 104
Value of Ka2: 10-7~10-8
N.Mohamed 32
Example:
2) Maleic acid;
Ka1= 1.2 x 10-2
Ka2= 4.7 x 10-7
2 end points
N.Mohamed 33
50.0 mL 0.100 M H2M is titrated
with 0.100 M NaOH. Calculate
the pH after adding 10.00,
50.00, 55.00, 100.00 and 110.00
mL base. For H2M,
Ka1= 1.0 x 10-3, Ka2 = 1.0 x 10-7
Addition 10.0 mL NaOH
H2M + NaOH NaHM + H2O
Initial, mmol 5.00 1.00 0 0
Equil, 4.00 0 1.00 1.00
buffer solution
pH = p Ka1 + [NaHM]
[H2M]
= 3.00 + log 1.00
4.00
= 2.40
N.Mohamed 34
Addition of 50.0 mL NaOH
amphoteric salt
[H+] = Ka1Ka2
pH = (pKa1 + Ka2) = (3.00+7.00)
= 5.00
N.Mohamed 35
Addition 55.0 mL NaOH
H2M + NaOH NaHM + H2O
Initial, mmol 5.00 5.50 0 0
Equil, 0 0.5 5.00 5.00
NaHM + NaOH Na2M + H2O
Initial, 5.00 0.50 0 0
Equil, 4.50 0 0.50 0.50
buffer solution
pH = p Ka2 + [Na2M]
[NaHM]
= 7.00 + log 0.50
4.50
= 6.05
N.Mohamed 36
Addition of 100.0 mL NaOH
H2M + NaOH NaHM + H2O
Initial, mmol 5.00 10.00 0 0
Equil, 0 5.00 5.00 5.00
NaHM + NaOH Na2M + H2O
Initial, 5.00 5.00 0 0
Equil, 0 0 5.00 5.00
N.Mohamed 38
We
Westart
startwith
withaaweak
weakacid,
acid,HH22A,
A,followed
followedby
byaabuffer
bufferregion
regionof
of
HA- and H A.
-
HA and H2 A. 2
([H+] ]constant).
The - +
Thefirst
firstequivalence
equivalencepoint
pointisisHA
HA-([H constant).
Then 2-/ - 2-
Thenwe wehave
haveaaAA2-/HA
HA-buffer
bufferregion,
region,andandAA2-(a (afairly
fairlystrong
strong
base) at the second equivalence point, followed
base) at the second equivalence point, followed by excess by excess
titrant.
titrant.
N.Mohamed 40
Gary Christian, Analytical Chemistry, 6th Ed.
(Wiley)
TITRATION OF MIXTURES OF
ACIDS-BASES
Can be titrated if the ratio of
Ka or Kb 104
HOAc, Ka = 1.75x10-5
Propionic acid, Ka = 1.30x10-5
N.Mohamed 41
A mixture of HCL and H3PO4 was
titrated using 0.100 M NaOH. 35.0
mL titrant was required to reach the
first equivalence point, and 15.0 mL
more of titrant for the second
equivalence point. Calculate
the mmol HCL and H3PO4 in
solution.
mmol(H3PO4+HCl)=35.0mLx0.100M
= 3.5 mmol.
N.Mohamed 42
The
Thestrong
strongacid
acidtitrates
titratesfirst.
first.
At
At its equivalence point, wehave
its equivalence point, we haveaamixture
mixtureof
ofNaCl
NaCland
andHOAc,
HOAc,and
andthe
the
pH is acidic.
pH is acidic.
This -
Thisisisfollowed
followedby
byaabuffer
bufferregion
regionof
ofOAc
OAc-and
andHOAc,
HOAc,and
-
andthenthenthe
the
HOAc equivalence point,
HOAc equivalence point, where we have OAc ,- a weak base.
where we have OAc , a weak base.
The -5
Theweak
weakacid
acidKKa amust
mustbe
beno
nolarger
largerthan
than10
10-5to
togive
giveaasharp
sharpsecond
secondend
end
point.
point.
For 4 or more.
Fortwo
twoweak
weakacids,
acids,the
theKKas
a sshould
shoulddiffer
differby
by10
104 or more.
N.Mohamed 44
Start: pH determined by hydrolysis of
Bronsted base, CO32-
After starting till before first equiv. point:
CO32- / HCO3-
1st buffer region
First equivalence point
NaHCO3
N.Mohamed 45
We 2-, a quite strong base. Then we have a HCO -/CO 2- buffer.
Westart
startwith
withCO
CO3 32-, a quite strong base. Then we have a HCO3 3-/CO3 32- buffer.
At the first equivalence point, we have HCO3- ([H +] = K K ).
At the first equivalence point, we have HCO3- ([H+] = K a1 K
a1 a2).
a2
Then -
Thenwewehave
haveaaHCO
HCO3 /H
3
2CO
-/H
2 CO3 buffer,
3 buffer,and
andHH
2CO
2 CO3 atatthe
3 thesecond
secondequivalence
equivalencepoint.
point.
The first e.p. is used to approximate the second, which is more accurately used.
The first e.p. is used to approximate the second, which is more accurately used.
Gary Christian,
Analytical
Chemistry, 6th
Ed. (Wiley)
Gary
Christian,
Analytical
Chemistry, 6th
Ed. (Wiley)
Titration of 50 mL N.Mohamed
0.1 M Na2CO3 with 47
0.1 M HCl using methyl red indicator.
Back titration
Reagent is added in excess to
sample. After rxn is
completed, amount of reagent
that is in excess (unreacted) is
titrated.
Mmol reagent reacted = mmol
(original back titrated)
Especially useful for:
Volatile reaction products.
Slow reactions.
Unstable reagents.
N.Mohamed 48
Determination of Cl-
Back titration:
Cl- + Ag+ (known) AgCl(s)
Ag+ (excess) + SCN- (titrant)
AgSCN (s)
N.Mohamed 49
Back titration
N.Mohamed 50
Solution ..
N.Mohamed 51
Kjeldahl analysis
Meat 6.25
Dairy products 6.38
Cereal 5.70
N.Mohamed 52
N.Mohamed 53
p.435
Kjeldahl analysis
N.Mohamed 55
Solution
N.Mohamed 56
END
N.Mohamed 57