Analytical Chemistry 1
Analytical Chemistry 1
Analytical Chemistry 1
Lecture 1
What is Analytical Chemistry?
Analytical chemistry is concerned with the
.chemical characterization of matter
Classification of Analytical Chemistry
Accuracy Precision
Accuracy : is the degree of agreement between
a measured value and a true (an expected)
.value
."تشير الدقة إلى مدى تقارب القيمة المقاسة للكمية مع قيمتها "الحقيقية
Precision: is the degree of agreement between
replicate measurements of the same quantity and
.does not necessarily imply accuracy
Examples
Consider the hydrolysis of urea in the presence of the )1(
.enzyme urease
Urease
NH2CONH2 + 2H2O + H+
-
2NH4+ + HCO3
Pyrocatechol violet is a specific indicator for Bi3+ in acidic )2(
solutions (pH 1-3)
+
2M + L1 M2L1 Blue + 3H
+
M2L1 + EDTA M-EDTA + L1 + 3H
Blue titrant (complexing agent) complex yellow
Selectivity: A selective reaction is one that can occur with
other substances but exhibits a degree of preference for the
substance of interest. Few reactions are specific but many
.exhibit selectivity
Examples
Note
If the measured value is the average of several
measurements and the error is called the mean error
Relative error ]2[
The absolute or mean error expressed a percentage
.of the true value is the relative error
√ ( 𝑥 1 − 𝑥 ) 2 +( 𝑥 2 − 𝑥 ) 2 + …
=S
𝑛 −1
The variance: is the square of the standard deviation
: Coefficient of variation (C.V)
is a more accurate measure of the precision
C.V = S × 100
X
±= √ 0.0020
0.045 ± =
F = S2 A / S 2 B Where S 2 A > S2 B
Example: The standard deviation from one set of 11
determinations SA = 0.210, and the standard deviation from
another 13 determinations was SB = 0.641. Calculate the
.value of F
F = S2 B / S 2 A
F = (0.641)2 / (0.210)2
9.4 =
Student’s t-test )b(
It is used for small samples; its purpose is to compare the
.mean from a sample with some standard value
Example
If X the mean of 12 determinations = 8.37, and
t 9.4 =
Acid – base titrations
Titrant
Titrand
The choice of indicators
Me.R Me. O Ph.ph Indicator
Equivalence Point
Before titration
HA -
H+ + A Where [H+] = [A-]
conjugate base
Ka = [H+] [A-]
]HA[
acid dissociation constant
Since [H+] or [ A-] is too small in comparison with [HA] then [HA]
: represents the conc. of the weak a cid, C, thus
2
= Ka C]+H[
1/2
)Ka C( = ]+H[
Ka [HA] / [A -
] = ]+H[
Ka [acid] / [salt] =
pH= pKa – log [[acid] / [salt]]
Henderson-Hasselbach equation
volume of alkali added = ]salt[
pH = pkw – pOH
After the end point
pH = ½ (pK1 +pK2)
pH = ½ (2.85+5.66) = 4.25
pH = ½ (pK1 +pK2)
pH = pkw – pOH
Example
In titrating 10 mL 0.1 M H2C2O4 with 0.1 M NaOH at the end point
(after adding 10 ml 0.1 NaOH). Ka = 6.1× 10-5
pH = ½ (pK2 +pK3)
-
PO43- + 3 H2O = H3PO4 + 3OH pH = 13
Before titration
1/2
)Kb C( = ]-OH[
1/2
)]salt[) Kw/Kb(( = ]+H[
Before titration
1/2
)Kb C( = ]-OH[
1/2
)1.8× 10-5 × 0.1( = ]-OH[ 10-3 ×1.3 =
mole/L 10-4 ×5 =
Example
M acetic acid with 0.1 M NH4OH 0.1
The titration curve has no sharp inflections at the end point
and therefore, no simple acid-base indicator will give a
sudden change of colour at this point
Displacement titrations
This type of titration can be used in case of salts derived from a
weak acid and a strong base
e.g. NaCN
+
Fe2+ = 2e- + 2 Fe3 2 Cl2 + 2e- = 2 Cl
-
Reductant oxidant
Reducing agent oxidizing agent
Eq. Wt = Mw/x
Titration of H2O2 with KMnO4
⟶ H2O−2 + O20
2O2 −1
H
H2O2 can be reduced to H2O as well as it can be oxidised to O2 .
Hence, it can act as an oxidizing agent by itself getting reduced to H2
O as well as it can act as a reducing agent by getting oxidized to O2.
.Therefore, it can act as oxidizing as well as reducing agent
Eq.wt of KMnO4
In acidic medium
MnO4- + 8H+ + 5e- = Mn2+ + 4H2O
Mn7
+
Eq. Wt = Mw/5
In neutral or alkaline medium
-
MnO4- + 2H2O + 3e- = MnO2 + 4OH
Eq. Wt = Mw/3
MnO4 acts as a stronger oxidizing
agent than I2
This depends on the value of standard redox potential
-
I2 + 2e- = 2I EO = 0.54 volt
N N
Diphenylbenzidine violet
)III(
In presence of Fe(II)
Agreenish colour which change to violet when a slight excess of
.Cr2O72- is added just beyond the end point
Titrations involving iodine
Rationalize
Iodimetry should not be performed in alkaline solutions ]1[
Because I2 will disproportionate
I2 + 2OH- IO- + I- + H2O
dation state= 0 hypoiodate iodide
Oxidation state= 1 Oxidation state= -1
Iodimetry should not be performed in strong acid medium ]2[
The starch used for the end point detection tends to )a(
.hydrolize or decompose in strong acid
The reducing power of several reducing agents increases )b(
. in neutral solution
-
2H++ H3AsO3 + I2 + H2O H3AsO4 + 4I
+ 2 + [H+]]+H[
-
=S
√ 𝐾 𝑠𝑝
𝛼2
Fraction of the oxalate species present as C2O4 2
Problem: Calculate the solubility of AgBr in 0.10 M
ammonia solution
) Kf1 = 2.5× 103 , Kf2 = 1× 104 ,
= 4× 10-1(
+ kf1kf2[NH3]2 + Kf [NH3]
=S
+
√ 𝐾 𝑠𝑝
𝐵𝑂
Fraction of the silver species present as Ag
Detection of End point
Standard
Mohr's Method solution of
AgNO3
Standard KSCN
Pot. thiocyanate
+ Halid
Ag+ + X AgX ppt + excess Ag+ Titration reaction Known
excess
Excess Ag+ + SCN AgSCN BackTitration reaction AgNO3
Fe3+ +
indicator+
Fe3+ + SCN Fe(SCN)2+ E.p reaction few drops
HNO3
Red color )ferrous thiocyanate(
Compleximetric reactions and titrations
H4Y (acid form of EDTA) have a very low solubility in water, and
.the disodium salt Na2H2Y.2H2O is usually used
+
Mn+ + H2Y2- MY (n-4) + 2H
+
Mg2+ + H2Y2- MgY (2-4) + 2H
+
Al3+ + H2Y2- AlY (3-4) + 2H
Precipitation Digestion
Preparation of the solution ترك الراسب فتره التمام الترسيب
Examples