0cddd9 Ch07 Let The Titrations Begin

1
Ch t 07 Chapter 07
Let the Titrations Begin
2007/10/31 QCA7e Chapter07 TMHsiung@2007 1/42
Contents in Chapter07
1. Overview of Titrimetry
2. Grades of Chemicals
3. Titration Calculations
4. Precipitation Titrations
1) Titration curve
2) Argentometric titration
5. Establish Precipitation Titration Curves with a
Spreadsheet
2
1. Overview of Titrimetry
1) Define Titration:
Titrations (or titrimetric method) are based on
measuring the amount of a reagent of known
concentration that reacts ith the nkno n concentration that reacts with the unknown.
A general equation can be expressed:
aA + tT products
A: analyte
T: titrant
2) Revisiting Keywords of Titration
Equivalence point: The point (e.g., volume of titrant)
in a titration where (theoretically) stoichiometrically
equivalent amounts of analyte and titrant react.
Indicator: Acolored compo nd hose change in Indicator: A colored compound whose change in
color signals the (experimental) end point of a
titration.
End point: The point (e.g., volume of titrant) in a
(experimental) titration where we stop adding titrant
in an experiment.
in an experiment.
Titration error: The determinate error in a titration
due to the difference between the end point and the
equivalence point.
3
3) Type of Titrations based on Chemical Reactions
i) Acid-Base Titrations, example:
H
+
+ OH
H
2
O K= 1/K
w
ii) Precipitation Titrations, example:
Ag
+
+ Cl
AgCl K 1/K Ag
+
(aq)
+ Cl
(aq)
AgCl
(s)
K=1/K
sp
ii) Redox Titrations:
5 H
2
O
2
+ 2 MnO
4
+ H
+
5 O
2
+ 2 Mn
2+
+ 8H
2
O
iv) Complexometric Titrations, example:
EDTA + Ca
2+
(CaEDTA)
2+
4) Type of Titrations based on Measuring
Techniques
i) Volumetric titrimetry: Measuring the volume of a
solution of a known concentration (e.g., mol/L) that
is needed to react completel ith the anal te is needed to react completely with the analyte.
ii) Gravimetric (weight) titrimetry: Measuring the
mass of a solution of a known concentration (e.g.,
mol/kg) that is needed to react completely with the
analyte.
iii) Coulometric titrimetry: Measuring total charge
iii) Coulometric titrimetry: Measuring total charge
(current x time) to complete the redox reaction, then
estimating analyte concentration by the moles of
electron transferred.
4
5) Type of Titration Curves
Type Example. y-axis x-axis
Acid-base HCl/NaOH pH V. NaOH
Precipitation Ag
+
/Cl
pAg
+
V Ag
+
Precipitation Ag
+
/Cl pAg
+
V. Ag
+
Complexation Ca
2+
/EDTA pCa
2+
V. EDTA
Redox MnO
4
/Fe
2+
Potential V. Fe
2+
Type Example y-axis x-axis
Spectro-
photometric
apotransferrin/
Fe
3+
Absorbance V.
Fe
3+
Thermo-
metric
H
3
BO
4
/
NaOH
Temperature V.
NaOH
2. Grades of Chemicals
1) Terms and Definitions
Reagent Grade: The reagents which meets or
surpasses the latest American Chemical Society
specifications specifications.
Primary standard: The reagent which is ready to be
weighted and used prepare a solution with known
concentration (standard).
Requirements of primary reagent are:
- Known stoichiometric composition
Known stoichiometric composition
- High purity
- Nonhygroscopic
- Chemically stable both in solid and solution
- High MW or FW
5
Secondary standard: A standard which is
standardized against a primary standard.
Certified reference materials (CRM): A reference
material, accompanied by a certificate, which has
been anal sed b different laboratories to determine been analysed by different laboratories to determine
consensus levels of the analyte concentration.
NIST Standard Reference Material
(SRM): A CRM
issued by NIST that also meets additional NIST-
specific certification criteria and is issued with a
certificate.
http://ts.nist.gov/MeasurementServices/ReferenceMaterials/USI
NG CATALOG f
certificate.
Standardization: The process by which the
concentration of a reagent is determined by reaction
with a known quantity of a second reagent
NG_CATALOG.cfm
3. Titration Calculations
1) Terms and Definitions:
Blank Titration: Titration procedure is carried out
without analyte (e.g., a distilled water sample). It is
d t t tit ti used to correct titration error.
Back titration: A titration in which a (known)
excess reagent is added to a solution to react with
the analyte. The excess reagent remaining after its
reaction with the analyte, is determined by a
titration
titration.
6
Example: To standardizing a KMnO
4
stock solution, the primary
standard of 9.1129 g Na
2
C
2
O
4
is dissolved in 250.0 mL volumetric
flask. 10.00 mL of the Na
2
C
2
O
4
solution require 48.36 mL of
KMnO
4
to reach the titration end point. What is the molarity (M) of
2) Standardization
KMnO
4
to reach the titration end point. What is the molarity (M) of
MnO
4
stock solution? (FW Na

2
C
2
O
4
134.0)
Solution:

4 2 2
2
4 2
4 2 2
4 2 2 4 2 2
mL 250
mL 10
O C Na mol 1
O C mol 1
O C Na g 134.0
O C Na mol 1
1
O C Na g 9.1129
5C
2
O
4
2
(aq)
+ 2MnO
4
(aq)
+ 16H
+
(aq)
10CO
2(g)
+ Mn
2+
(aq)
+ 8H
2
O
(l)
=
4
2
4 2
4
MnO 02250 . 0
L 1
mL 1000
mL 48.36
1
O C mol 5
MnO mol 2
M
Ans
Example: A 0.2865 g sample of an iron ore is dissolved in acid, and
the iron is converted entirely to Fe
2+
. To titrate the resulting solution,
0.02653 L of 0.02250 M KMnO
4
is required. Also a blank titration
require 0.00008 L of KMnO
4
solution. What is the % Fe (w/w) in
3) Unknown Analysis with a Blank Correction
q
4
( )
the ore? (AW Fe 55.847)
Solution:
MnO
4
(aq)
+ 5Fe
2+
+ 8H
+
(aq)
Mn
2+
(aq)
+ 5Fe
3+
+ 4H
2
O
(l)
5 02250 . 0 02645 . 0
02645 . 0 00008 . 0 02653 . 0
2
4
Fe mol MnO mol titrant L
L L vol titrant Net

= =
+
) / ( % 01 . 58 % 100
2865 . 0
1
1
847 . 55
1 titrant L 1 1
2
4
w w Fe
sample g Fe mol
Fe g
MnO mol
=

+
Ans
7
4) Back Titration
Example: The arsenic in 1.010 g sample was pretreated to
H
3
AsO
4(aq)
by suitable treatment. The 40.00 mL of 0.06222 M
AgNO
3
was added to the sample solution forming Ag
3
AsO
4(s)
:
) ( 4 3
) ( ) (
) ( 4 3
3 3
s
aq aq
aq
AsO Ag H Ag AsO H + +
+ +
Solution:
The excess Ag
+
was titrated with 10.76 mL of 0.1000 M KSCN. The
reaction was:
Calculate the percent (w/w) As
2
O
3(s)
(fw 197.84 g/mol) in the
sample.
) ( 4 3
) ( ) (
) ( 4 3 s
q q
aq
g g
) (
) ( ) (
s
aq aq AgSCN SCN Ag +
+
mL x M = mmol
Total mmol Ag
+
added
= (mmol Ag
+
consumed by SCN
) + (mmol Ag
+
consumed by H
3
AsO
4
)
0760 1
1 1000 . 0
76 10

4888 . 2
1
06222 . 0
00 . 40
3
3
3
Ag mmol
Ag mmol SCN mmol
mL SCN
SCN by consumed mmol Ag
mmol
AgNO mL
AgNO mmol
AgNO mL
added mmol Ag Total
= =
= =
+
+
+
+
3 0760 . 1 4888 . 2
3
1
3

0760 . 1
1
76 10
4 3
4 3
4 3
Ag mmol x Ag mmol Ag mmol
Ag mmol x
AsO H mmol
Ag mmol
AsO mmol H x
AsO H mmol x by consumed mmol Ag
Ag mmol
SCN mmol SCN mL
mL SCN .
+ =
= =
= =
+ + +
+
+
+

(w/w) % 612 . 4 % 100
010 . 1
1
1
84 . 197
1000
1
2
1

1
1
1
4709 . 0

4709 . 0
3 2
3 2
3 2
3 2
3 2 3 2
4 3
4 3
4 3 4 3
O As
sample g O As mol
O As g
O As mmol
O As mol
As mmol
O As mmol
AsO H mmol
As mmol AsO H mmol
AsO H mmol AsO H mmol x
=

=
Ans
8
5) Kjeldahl Analysis () for Total Nitrogen (TN)
i) KD description:
Step 1: Kjeldahl digestion (decomposing and dissolving)
Organic N NH CO H O
H SO (K S O )
Hg or Cu or Se
4 2 2
2 4 2 2 8
+ +
+
Organic N NH CO H O
4 2 2
+ +
O H NH OH + NH
2 3(g) 4
+
+
NH + H O NH H O
3(g) 3
+
4 2
+
+
Step 2: Neutralization by adding base
Step 3: Distillation NH
3
into excess HCl standard
3(g) 3 4 2
O H 2 OH O H
2
+
3
+

Step 4: Titrating unreacted HCl with NaOH standard
PowerPoint [] []
:,,
,
: (
,)"",
, ,
,
"",
Protein + H2SO4 CO2 + (NH4)2SO4 + SO2

(NH4)2SO4 + 2NaOH Na2SO4 + NH4OH
2NH4OH + H2SO4 (NH4)2SO4 + 2H2O
Kjeldahl methodJohan Kjeldahl 1800
9
Example: A typical meat protein contains 16.2% (w/w) nitrogen.
A 0.500 mL aliquot of protein solution was digested, and the
liberated NH
3
was distilled into 10.00 mL of 0.02140 M HCl.
The unreacted HCl required 3.26 mL of 0.0198 M NaOH for
complete titration. Find the concentration of protein (mg
protein/mL) in the original sample.
Solution:
H l
H mmol OH mmol
N OH L
satndard NaOH by consumed mmol H
H mmol
HCl mL
H mmol
HCl mL
added mmol H Total
0645 0
1 0198 . 0
26 3

2140 . 0
1
02140 . 0
00 . 10 = =
+
+
+
+
+
+
N d d l N d d l
H mmol x H mmol H mmol
H mmol x
N digested mmol
H mmol
N digested mmol x
N digested mmol x by consumed mmol H
H mmol
OH mmol NaOH mL
NaOH mL
1495 0
0645 . 0 2140 . 0

1
1

0645 . 0
1 1
26 . 3
+ =
= =
= =
+ + +
+
+
+
+

mL protein mg
sample mL
N mg
protein mg
N mmol
N mg
N digested mmol
N digested mmol N digested mmol x
/ 8 . 25
5 . 0
1
2 . 16
100

1
00674 . 14
1495 . 0
1495 . 0
=

=
Ans
10
6) Titration of a Mixture
Example: A solid mixture weighing 1.372 g containing only
sodium carbonate (Na
2
CO
3
, FW 105.99) and sodium bicarbonate
(NaHCO
3
, FW 84.01) require 29.11 mL of 0.7344 M HCl for
complete titration: p
Find the mass of each component of the mixture.
Solution:
2 2 ) ( 3
2 2 ) ( 3 2
2 2
CO O H NaCl HCl NaHCO
CO O H NaCl HCl CO Na
aq
aq
+ + +
+ + +
3 2
3 2
2 2 1

02138 . 0
1
7344 . 0
000 1
1
11 . 29
H mol
x H mol CO Na mol
CO Na g x
CO Na by consumed mmol H
H mol
HCl L
H mol
mL
L
HCl mL
added mmol H Total
|
|
|
= =
= =
+
+
+
+
+
+
3 3
3
3
3
3 2 3 2
3 2
01 . 84
372 . 1
99 . 105
2
02138 . 0

01 . 84
372 . 1
1
1
01 . 84
1
) 372 . 1 (

99 . 105 1 99 . 105
x x
H mol
x
NaHCO mol
H mol
NaHCO g
NaHCO mol
NaHCO g x
NaHCO by consumed mmol H
H mol
CO Na mol CO Na g
CO Na g x
|
.
|
\
|

+
|
.
|
\
|
=
|
.
|
\
|

= =
|
.
\
= =
+
+
+
3 3
3 2 3 2
648 . 0 ) 372 . 1 (
724 . 0
NaHCO g NaHCO g x
CO Na g CO Na g x
=
=
Ans
Ans
11
4. Precipitation Titrations
A titration in which the reaction between the
analyte and titrant involves a precipitation.
1) Tit ti 1) Titration curve
i) Guidance in precipitation titration calculation
Find V
e
(volume of titrant at equivalence point)
Find y-axis values:
- At beginning
- Before V
Before V
e
- At V
e
- After V
e
Example: For the titration of 50.0 mL of 0.0500 M Cl
with 0.100
M Ag
+
. The reaction is:
Ag
+
(aq)
+ Cl
(aq)
AgCl
(s)
K = 1/K
sp
= 1/(1.810
10
) = 5.6 x 10
9
Find pAg and pCl of Ag
+
solution added
(a) 0 mL (b) 10.0 mL (c) 25.0 mL (d) 35.0 mL
Solution:
12
(a) 0 mL Ag
+
added (At beginning)
[Ag
+
] = 0, pAg can not be calculated.
[Cl
] = 0.0500, pCl = 1.30

(b) 10 mL Ag
+
added (Before V
e
)
10 50 2
5 . 1
] [
0 . 60 0 . 10 0 . 50
50 . 1
1
1
1
100 . 0
0 . 10
1
0500 . 0
0 . 50

2
= =
= + =
=
|
|
.
|
\
|

|
|
.
|
\
|
=
=
+
+
+

M
Cl mmol
Cl
mL mL mL V
Cl mmol
Ag mmol
Cl mmol
Ag mL
Ag mmol
Ag mL
Cl mL
Cl mmol
Cl mL
Cl mmol ed precipitat Cl mmol original Left Cl mmol
total
14 . 8
60 . 1
10 2 . 7
10 50 . 2
10 8 . 1
] [
] [
10 50 . 2
0 . 60
] [
9
2
10
=
=
=
= =
= =
+
pAg
pCl
M
Cl
K
Ag
M
mL
Cl
sp
(c) 25 mL Ag
+
added (At V
e
)
AgCl
(s)
Ag
+
(aq)
+ Cl
(aq)
K
sp
= 1.810
10
s = [Ag
+
]=[Cl
]
K
sp
= 1.810
10
= s
2
[Ag
+
]=[Cl
]=1.35x10
5
[ g ] [ ]
pAg = 4.89
pCl = 4.89
13
(d) 35 mL Ag
+
added (After V
e
)
00 1
1
100 . 0
0 . 25
1
100 . 0
0 . 35

=
|
|
.
|
\
|

|
|
.
|
\
|
=
=
+
+
+
+
+
+
+
+ + + +
Ag mmol
Ag mL
Ag mmol
Ag mL
Ag mL
Ag mmol
Ag mL
Ag of withV Ag mmol ed precipitat Ag mmol original Left Ag mmol
e
82 . 7
10 53 . 1
10 18 . 1
10 8 . 1
] [
] [
10 18 . 1
0 . 85
00 . 1
] [
0 . 85 0 . 35 0 . 50
00 . 1
8
2
10
2
=
=
= =
= =
= + =
+
+
pCl
M
Ag
K
Cl
M
mL
Ag mmol
Ag
mL mL mL V
Ag mmol
sp
total
93 . 1 = pAg
ii) Construct a titration curve
Example: Titration of 50.0 mL of 0.0500 M Cl
with 0.100 M Ag
+
pCl
pAg
14
iii) End point determination
dy/dx
d
2
y/dx
2
iv) Diluting effect of the titration curves
25.00 mL 0.1000 M I
titrated with 0 05000 MAg

+
titrated with 0.05000 M Ag
25.00 mL 0.01000 M I

+
25.00 mL 0.001000 M I

+
15
v) K
sp
effect of the titration curves
25.00 mL 0.1000 M halide (X
)
+
(a) 40.00 mL of 0.0502
M KI + 0.0500 M
KCl titrated with
vi) Titration of a mixture (uncertainty concerned)
KCl, titrated with
0.0845 M Ag
+
(b) 20.00 mL of 0.1004
M KI titrated with
0.0845 M Ag
+
16
Example: A 25.00 mL solution containing Br
and Cl
was
titrated with 0.03333 M AgNO
3
. K
sp
(AgBr)=5x10
13
,
K
sp
(AgCl)=1.8x10
10
.
(a) Which analyte is precipitated first?
(b) The first end point was observed at 15.55 mL. Find the
i f h fi h i i d (B Cl ?) concentration of the first that precipitated (Br
or Cl
?).
(c) The second end point was observed at 42.23 mL. Find the
concentration of the second that precipitated (Br
or Cl
?).
Solution:
(a)
Ag
+
(aq)
+ Br
(aq)
AgBr
(s)
K = 1/K
sp
(AgBr) = 2x10
12
A
+
Cl A Cl K 1/K (A Cl) 5 6 10
9
Ag
+
(aq)
+ Cl
(aq)
AgCl
(s)
K = 1/K
sp
(AgCl) = 5.6x10
9
Ans: AgBr precipitated first
(b)
+
+
+
+ +
=

Br M 0.02073
L 1
mL 1000
mL 25
1
Ag mol 1
Br mol 1
Ag L 1
Ag mol 0.3333
mLAg 1000
Ag L 1
1
Ag mL 15.55
Ans
L 1 mL 25 Ag mol 1
(c)
+
+
+
+ +

Cl M 0 03557
mL 1000 1 Cl mol 1
Ag L 1
Ag mol 0.3333
mLAg 1000
Ag L 1
1
Ag mL 15.55) - (42.23
+
= Cl M 0.03557
L 1 mL 25 Ag mol 1
Ans
17
2) Argentometric Titration ()
1) General information:
Define Argentometric Titration: A precipitation
titration in which Ag
+
is the titrant.
A t t i Tit ti l ifi d b t f E d Argentometric Titration classified by types of End-
point detection:
Volhard method: A colored complex (back titration)
Fajans method: An adsorbed/colored indicator
Mohr method: A colored precipitate
1. (Mohr Method). 2. (Fajans Method). 3. (Volhard Method)
2) Volhard method (): A colored complex
(back titration). Analysing Cl
for example:
Step 1: Adding excess Ag
+
into sample
Ag
+
+ Cl
AgCl
(s)
+ left Ag
+
Step 2: Removing AgCl by filtration/washing Step 2: Removing AgCl
(s)
by filtration/washing
Step 3: Adding Fe
3+
into filtrate (i.e., the left Ag
+
)
Step 4: Titrating the left Ag
+
by SCN
:
Ag
+
+ SCN
AgSCN(s)
Step 5: End point determination by red colored
Fe(SCN)
2+
complex. (when all Ag
+
has been
( ) p ( g
consumed, SCN
reacts with Fe
3+
)
SCN + Fe
3+
Fe(SCN)
2+
(aq)
Total mol Ag
+
= (mol Ag
+
consumed by Cl
)
+ (mol Ag
+
consumed by SCN
)
18
3) Fajans Method (): An adsorbed/colored
indicator. Titrating Cl
and adding
dichlorofluoroscein for example:
Before V
e
(Cl excess)
Greenish
yellow solution
AgCl
(s)
Cl
1st
layer
After Ve
(Ag
+
excess)
AgCl
(s)
Ag
+
In
pink
1st
layer
4) Mohr Method (): A colored precipitate
formed by Ag
+
with anion, other than analyte, once
the V
e
reached. Analysing Cl
and adding CrO

4
2
for example:
Precipitating Cl
:
Ag
+
+ Cl
AgCl
(s)
K
sp
= 1.8 x 10
10
End point determination by red colored precipitate,
Ag
2
CrO
4(s)
:
2Ag
+
+ CrO
4
2
Ag
2
CrO
4(s)
K
sp
= 1.2 x 10
12
2Ag CrO
4
Ag
2
CrO
4(s)
K
sp
1.2 x 10
19
5) Applications of argentometric titrations:
5. Establish Precipitation Titration Curves with a
Spreadsheet
Example:
M
+
(aq)
+ X
(aq)
MX
(s)
K = 1/K
sp
i A l

X of vol. initial : V
X of conc : C
M of conc. : C
o
X
o
X
o
M
+
Titrant Analyte

added M of V when X of conc. : ] [X
added M of V when M of conc. : ] [M
added M of vol. : V
M
M
M
+
+ + +
+

20
(s)
o
X M M
o
M
X f b l M
MX mol ) V ](V [M V C
: M for balance Mass
+ + = -
+
1) Derive the equation:
moles of Min
)
] [X ] [M C
] [X ] [M C
( V V
o
M
o
X o
X M
+
+
+
+
=
(s)
o
X M
o
X
o
X
MX mol ) V ](V [X V C
: X for balance Mass
+ + = -

moles of M in
precipitate
moles of X in
precipitate
] [ ] [
M
Mass balance: The moles of an element in all
species in a mixture equal to the total moles of that
element delivered to the solution.
)
] [X ] [M C
] [X ] [M C
( V V
o
M
o
X o
X M
+
+
+
+
=
2) Apply the equation:
K and V C C : es known valu in Key 1
o
X
o
X
o
M
] [M
K
] [X ], [X Calculate 4.
10 ] [M ], [M Calculate 3.
pM Input 2.
K and , V , C , C : es known valu in Key 1.
sp
pM
sp X X M
+

+ +
=
=
obtained V equation, into ] [X and ] [M Substitute . 5
] [M
M
+
21
3) Example: Construct a titration curve for the titration
of 50.0 mL of 0.0500 M Cl
with 0.100 M Ag
+
. (K
sp
of AgCl = 1.810
10
)
EXCEL
961_Ch07_Titration_X_with_Ag
22
Homework: Problem 7-30/p.139, Due 2007/11/7
Examples: Examples:
All
Exercise
A-E, G
End of Chapter07
Problems:
1-7, 11-14, 31, 36

0cddd9 Ch07 Let The Titrations Begin

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1

stock solution? (FW Na

Protein + H2SO4 CO2 + (NH4)2SO4 + SO2

2007/10/31 QCA7e Chapter07 TMHsiung@2007 18/42

] = 0.0500, pCl = 1.30

titrated with 0 05000 MAg

titrated with 0.005000 M Ag

titrated with 0.0005000 M Ag

and adding CrO

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