Sie sind auf Seite 1von 65

Pharmaceutical Analytical Chemistry 1

Course Code:

1805323

Lecturer: Dr. Afaf Osman Course Schedule:

Lecture: Thursday 3 rd & 4 th

INTRODUCTION

References:

Analytical Chemistry, Gary D. Christian, Publisher: Wiley; 6th edition.

Fundamentals of Analytical Chemistry, Douglas A. Skoog, Donald M. West, F. James Holler, Stanley R. Crouch, Publisher: Brooks Cole; 8th edition.

Recommended reading / resources

Analytical chemistry, An introduction, Douglas A. Skoog, Donald M. West, F. James Holler, Stanley R. Crouch, Publisher: Brooks Cole; 6th edition.

Dean's Analytical Chemistry Handbook , Pradyot Patnaik, Publisher: McGraw-Hill Professional.

Quantitative Chemical Analysis , Daniel C. Harris, Publishers: W.H. Freeman and Company;8th Edition. Methods of Assessment:

Mid-Term Exam 20%

Final exam 50% (out of 60% in case of only theory courses)

Laboratory work, presentation and seminars 20%

Other academic activities 10% (20% in case of only theory courses)

Pass Requirements The aggregate mark must surpass the pass/fail boundary, which is 60%.

9/22/2014

Quantitative analysis

Quantitative analysis deals with the determination of the quantity of the

substance to be analyzed. Methods of quantitative analysis may be classified according to:

1- The quantity measured,

2- Physical state of the substance to be analyzed and

3- The process of measurement.

Classification according to the quantity measured
Classification according to the quantity measured

Semi-micro analysis

Micro-analysis

Macro-analysis

Measuring quantity starting from 100mg and more

Measuring quantity ranging

from 10-100mg

Measuring quantity not exceeding 1mg

ranging from 10-100mg Measuring quantity not exceeding 1mg Classification-according to the physical state of the

Classification-according to the physical state of the substance to be analyzed.

Gas analysis

state of the substance to be analyzed. Gas analysis Kind of the analyzed material Substance in

Kind of the analyzed material

to be analyzed. Gas analysis Kind of the analyzed material Substance in gaseous state Food analysis
to be analyzed. Gas analysis Kind of the analyzed material Substance in gaseous state Food analysis

Substance in gaseous state

Food analysis

Water analysis

9/22/2014

Classification according to the process of measurement Gravimetric analysis Volumetric analysis Instrumental methods of

Classification according to the process of measurement

Gravimetric analysis
Gravimetric
analysis

Volumetric analysis

Instrumental methods of analysis

Formation weakly ionisable salt Complexation reactions Electron transfer reactions
Formation weakly ionisable salt
Complexation reactions
Electron transfer reactions

Neutralization reactions

Electron transfer reactions Neutralization reactions Formation of water Displacement titration Formation of weak

Formation of water

Displacement titration

reactions Formation of water Displacement titration Formation of weak acid Formation of weak base Gravimetric

Formation of weak acid

Formation of weak base

Gravimetric analysis:titration Formation of weak acid Formation of weak base • It is a quantitative method of

It is a quantitative method of analysis by weighing the final product of reaction after its isolation in pure and stable form of definite chemical structure.

Instrumental methods of analysis:in pure and stable form of definite chemical structure. • Are physico-chemical methods, depend mainly on

Are physico-chemical methods, depend mainly on optical and electrical properties. By measuring these

Volumetric Analysis: • Depends on measuring the volume of the analyzed sample and the volume

Volumetric Analysis:

Depends on measuring the volume of the analyzed sample and the volume of standard solution used for complete reaction.

This process is known as Titration . Which means the capacity of the sample to combine with the suitable standard quantitatively through quantitative reaction.

Quantitative reaction , is that reaction which proceed forward to produce

stable products such as weakly ionisable compounds, H 2 O, weak acid, weak base, sparingly soluble salts (Precipitate), complex ion, etc.

Volumetric Analysis Classified Into The Following Types:

A- Neutralization reactions:

1- Formation of water

Water is produced as a result of interaction between acid and base, which involves combination between hydrogen ion and hydroxyl ion to form very weakly ionisable

water.

Acid + Base H + + OH -

2- Displacement titration:

a- Formation of weak acid.

Water + Salt H 2 O

Salt of weak acid + strong acid weak acid + salt of strong acid.

KCN + HCl

HCN + KCl

Na 2 B 4 O 7 .5H 2 O + 2 HCl

4H 3 BO 3 + 3NaCl.

9/22/2014

b- Formation of weak base:

Salt of weak base + Strong base

AlCl 3 + 3 NaOH NH 4 Cl + NaOH

weak base + salt of strong base AL(OH) 3 + 3 NaCl NH 4 OH + NaCl

B. Formation weakly ionisable salt : { ppt} :

Reaction between mercuric nitrate (Hg(NO 3 ) 2 ) or AgNO3 with Cl - .

Ag +

+

Cl -

Hg(NO 3 ) 2 + 2NaCl

C. Complexation reactions :

AgCl

Hg(NO 3 ) 2 + 2NaCl C. Complexation reactions : AgCl ( weakly ionised ) HgCl

(weakly ionised)

HgCl 2

(weakly ionised) + 2 NaNO 3

Reaction between silver ion (Ag + ) and cyanide ion (CN - ) to produce the weakly ionised complex ion, soluble K[Ag(CN) 2 ] Ag + + 2 CN - [Ag(CN) 2 ] -

Reaction between EDTA (H 2 y 2- ) and metal ion e.g. Ca 2+ to produce the weakly ionised complex or chelate (Cay 2- )

D.

Electron transfer

Ca 2+ + H 2 y 2- Cay 2- + 2H + reactions :

Transfer of electrons between reactants (oxidants and reductants) which is followed by change in the oxidation number of the reactants.

Ce 4+ + Fe 2+ Fe 3+ + Ce 3+

9/22/2014

Requirements of Titrimetric Reactions:

1.

The reaction must be simple and can be expressed by chemical equation.

2.

A single reaction must occur between the desired sample and titrant as described by corresponding chemical equation.

3.

The reaction must be instantaneous. If slow it must be catalyzed.

4.

Suitable standard solution must be available as titrant.

5.

The end point should be easily detected by visual indicator or an instrumental

method.

Volumetric methods are more commonly used as they are more quicker and easier methods if compared with gravimetric and physico-chemical methods.

In volumetric analysis we deal with the determination of the concentration of solution of a certain sample or the percentage of pure chemical in powdered sample. This can be achieved by the use of solutions of known concentrations, which are known as standard solutions.

Sta n dard Solu tions

They are solutions of exact and known concentration. They are classified according to the type of concentration into:

1 .

Molar Solution (M)

It is a solution of known concentration, each liter of which contain the gram molecular weight or fraction of the gram molecular weight or multiple of the gram molecular weight.

When the concentration is:

Molecular weight (M.wt) / liter (L), it is expressed as 1M or M ½ M.wt /L, it is expressed as M/2 or 0.5M solution. 4 M.wt/L, it is expressed as 4M solution.

M= n / v = no. of moles / volume (L) = no. of millimoles / volume ( ml) = wt(g) / MW× V (L) = wt mg / MW× V (ml)

2. Normal Solution (N)

It is a solution of known concentration, each liter of which contain the gram equivalent weight

(eq.wt) or fraction of the gram eq.wt or multiple of the gram eq.wt.

When the concentration is:

eq.wt / L, it is expressed as 1N or N solution. 1/ 10 eq.wt / L, it is expressed as 0.1N or N/10 solution. 3 eq.wt / L, it is expressed as 3N solution.

N = no. of equivalents / Volume (L) = no. of milliequivalents / Volume (ml)

e.g. Calculate molarity of a solution contain 6.0 gm of NaCl ( MW = 58.44 ) in 200 ml solution ?

M= 6.0 / 58.44 × 0.2 = 6000/ 58.44 × 200 = 0.513 mol/ L Or 0.513 m mol/ ml

e.g. Calculate normality of one liter of NaCl containing 5.85 gm of salt ( MW = 58.5)?

N = 5.58 / 58.5 × 1 = 0.1 N

gm of salt ( MW = 58.5 )? N = 5.58 / 58.5 × 1 =
gm of salt ( MW = 58.5 )? N = 5.58 / 58.5 × 1 =

If 12 gm of CaBr 2 is dissolved in 500 ml of water, determine its molarity? { Mw of CaBr 2 = 199.88 gm }

9/22/2014

Calculation of The Equivalent Weight of Different Electrolytes

Acids Eq.wt = (M.wt ) / number of replaceable hydrogen i.e. in case of :

=

H 2 SO 4 , eq.wt =

HCl, eq.wt

M.wt / 1 M.wt / 2

Bases

Eq.wt = (M.wt ) / number of replaceable hydroxyl ion

i.e. in case of :

NaOH,

eq.wt =

M.wt / 1

Ba(OH) 2 ,

eq.wt =

M.wt / 2

Salts

Eq.wt = M.wt / number of cations × its valency

Or

i.e. in case of

M.wt / number of anions × its valency

Na 2 SO 4 , eq.wt = M.wt / 2×1

or

M.wt / 1 × 2

2 SO 4 , eq.wt = M.wt / 2 × 1 or M.wt / 1 ×

Preparation o f standard solutions

a. Direct method: {A chemical is of primary standard quality}

An accurately weighed amount of the solute is transferred into a

volumetric flask, dissolved in the solvent then completed to the required volume and mixed well. The prepared solution is used as

exact standard.

9/22/2014

Primary Standard Chemicals

Primary standard chemicals are substances of definitely known composition and high purity.

They must fulfill the following requirements:

1.

They must be available in very high grade of purity and of known composition (A.R)

2.

They must be easily tested for impurity by simple test.

3.

They must be stable, i.e. not absorbing water (not be hygroscopic) or CO 2 from atmosphere, not volatile and withstand drying at 110-120 o C.

4.

They must react with other substances quantitatively according to a balanced chemical

equation. i.e. react stoichiometrically.

5.

They must be readily soluble in the solvent.

6.

They should have high equivalent weight to minimize weighing error.

Examples of primary standard chemicals:

Potassium hydrogen phthalate (KHC 8 H 4 O 4 ), benzoic acid (HC 7 H 5 O 2 ), constant-boiling- point hydrochloric acid, anhydrous sodium carbonate (Na 2 CO 3 ), anhydrous potassium bicarbonate (KHCO 3 )and mercuric oxide (HgO). potassium dichromate (K 2 Cr 2 O 7 )

9/22/2014

Secondary Standard Chemicals Secondary standard chemical is a standard that is prepared in the laboratory for a specific analysis and whose content have been found by comparison against primary standard. Examples of secondary standard chemicals:

e.g. borax (Na 2 B 4 O 7 .10H 2 O) and oxalic acid (H 2 C 2 O 4 .2H 2 O).

b. Indirect method:

If the solute is not primary standard, it is used to prepare solution of approximate concentration [secondary standard solution], and its exact concentration is determined

by a process known as Standardization against primary standard solution.

Standardization factor (f) = volume of exact standard / volume of approximate standard = volume of known normality / volume of unkown normality

NaOH

of known normality / volume of unkown normality NaOH • f express, how much of exact

f express, how much of exact is present in the approximate.

f ranges from 0.95-1.05, out this range the solution is not of expected strength. - The volume of secondary standard must be multiplied by its standardization

factor (f ) to obtain the volume of St. soln. of exact normality or molarity.

What volume of a 0.1 M HCl solution is needed to neutralize 25 ml of 0.35 M

NaOH ?

HCl + NaOH

M = n / V

n = number of moles V = volume

n = V × M

NaCl + H 2 O

Number of moles of NaOH = 25 × 0.35 = 8.75 m moles

n of NaOH = n of HCl since reaction is 1 : 1 = 8.75 m mloes

M × V of HCl = 8.75 0.1 × V = 8.75 V = 87.5 ml

N 1 ×

V 1

= N 2 × = 0.35

V 2

0.1

×

V 1

× 25

V 1 = 87.5 ml

9/22/2014

Acid- Base (Neutralization) Titrations

Acid-Base titrations In Aqueous Medium

Acid- Base (Neutralization) Titrations Acid-Base titrations In Aqueous Medium 9/22/2014 14

9/22/2014

Acids & BasesTheories

Acids:

Arrhenius acid: Any substance that, when dissolved in water, increases the concentration of hydronium ion (H 3 O + ) or Substances which ionize to give H + ions in solution. (H 2 SO 4 & HCl)

Bronsted-Lowry acid: A proton donor i.e substance which loss or donate proton

Lewis acid:

An electron acceptor i.e. accept lone pair of electrons. (AlCl 3 , BF 3 )

Bases:

Arrhenius base: Any substance that, when dissolved in water, increases the concentration of hydroxide ion (OH - ) or Substances which ionize to give hydroxide ions (OH - ) in solution. (NaOH)

Bronsted-Lowery base: A proton acceptor i.e substance which gains or accepts proton

Lewis base:

An electron donor i.e donates lone pair of electrons. ( NH 3 , amines)

9/22/2014

1- Arrhenius theory (Electrolytic Dissociation Theory) :

Acid : Is the substance which ionize to give H + Base : Is the substance which ionize to give OH -

eg. HCl

eg NaOH

This theory didn't discuss the role of solvent in the ionization process.

There are some points of weakness in electrolytic dissociation theory as:

HCl- gas has no acidic properties on dry litmus paper

Ammonia NH

theory. Since there is no hydroxyl group present in the ammonia (NH 3 ) molecule, But ammonia shows basic nature

Ammonia reacts with the water it is dissolved in to produce ammonium ions and hydroxide ions:

NH 3

i.e. the basic characters are due to the formation of compounds which release OH - .

3

and amines R-NH , are not base according to the Arrhenius acid-base

2

+ H 2 O

not base according to the Arrhenius acid-base 2 + H 2 O NH 4 OH NH

NH 4 OH

to the Arrhenius acid-base 2 + H 2 O NH 4 OH NH 4 + +

NH 4 + +

OH -

1- Arrhenius theory

During dissociation of an acid in water, H

electric charge is very intense, therefore, it cannot exist independently in solution. It will be attracted to oxygen of water, due to the presence of two unshared pair of

electrons.

Electric charge (F)

Where: Q =

F in case of H + is very intense, due to its very small radius therefore protons are hydrated or generally solvated with solvent molecules

+ be liberated. H

+

is very small in size, its

Q/m m = radius of mass.

charge

H + + H 2 O:

H + is very small in size, its Q/m m = radius of mass. charge H

H 3 O +

hydronium ion

Acid

Acid

Acid

2- Bronsted - Lowry theory :

Acid : Is the substance which donate proton.

Base : Is the substance which accept proton.

N.B.
N.B.

Eg.

HCl

+

Acid

Eg.

NH 3

+

base

H 2 O base 2 O base

H 2 O acid 2 O acid

Cl - conj. base
Cl -
conj. base

+

+ base H 2 O base H 2 O acid Cl - conj. base + NH

NH 4 + conj. acid

+

H 3 O + conj. acid

OH -

conj. base

- The solvent, in this theory, is involved in the reaction as acid or base,

- Every acid has a conjugate base and the base has conjugate acid.

- The stronger the acid the weaker its conjugate base and vice versa.

- Water behaves as acid or base because it is neutral (amphoteric)

18

the weaker its conjugate base and vice versa . - Water behaves as acid or base

BRONSTED - LOWRY

THEORY

When an acid gives up a proton, the remaining species has a certain proton affinity and hence is a base. This base known as the conjugate base of the acid, and the two forms are known as an acid-base pair.

acid

HA

+

base

B -

conjugate

known as an acid-base pair. acid HA + base B - conjugate base A - conjugate

base

A -

conjugate

+

acid

BH

acid HA + base B - conjugate base A - conjugate + acid BH -H +
acid HA + base B - conjugate base A - conjugate + acid BH -H +

-H +

+H +

acid = proton donor base = proton acceptor

HA + base B - conjugate base A - conjugate + acid BH -H + +H

9/22/2014

The Cl - is the conjugate base of the acid HCl,

The Ac - is the conjugate base of the acid HAc - and

The H + (H 3 O + ) is the conjugate acid of the H 2 O.

The stronger the acid, the weaker its conjugate base and vice versa.

Acid (A 1 )

 

Base(B 2 )

Conj-Acid(A 2 )

Conj-Base(B 1 )

HCl

+

H

2 O

HCl + H 2 O H 3 O + + Cl -

H

3 O +

+

Cl -

NH 4 +

+

H

2 O

NH 4 + + H 2 O H 3 O + + NH 3

H

3 O +

+

NH 3

HSO 4 -

+

H

2 O

HSO 4 - + H 2 O H 3 O + + SO 4 2 -

H

3 O +

+

SO 4 2-

Base 1

Acid 2

Conj-Base 2

 

Conj-Acid 1

NH 3

+

H

2 O

NH 3 + H 2 O OH - + NH 4 +

OH -

+

NH 4 +

CH 3 COO -

+

H

2 O

CH 3 COO - + H 2 O OH - + CH 3 COOH

OH -

+

CH 3 COOH

HPO 4 2-

+

H

2 O

HPO 4 2 - + H 2 O OH - + H 2 PO 4 -

OH -

+

H 2 PO 4

-

9/22/2014

Conjugate Acid-Base Pairs

Conjugate Acid-Base Pairs 9/22/2014 21
Conjugate Acid-Base Pairs 9/22/2014 21

9/22/2014

Classification of Acids and Bases According to Bronsted- Lowery Concept

Acids.
Acids.

Charged acids

According to Bronsted- Lowery Concept Acids. Charged acids Anionic acids. e.g. HSO 4 - , H

Anionic acids. e.g. HSO 4 - , H 2 PO 4

-

e.g.

Bases

acids. e.g. HSO 4 - , H 2 PO 4 - e.g. Bases Neutral molecules (uncharged

Neutral molecules (uncharged acids)

e.g. HCl, H 2 SO 4 , HClO 4 CH 3 COOH, HCOOH

Neutral molecules (uncharged bases)

e.g. NH 3 , R-NH 2 , R 2 -NH, R 3 -N

Charged bases (Anionic bases)

e.g, CH 3 COO - , HCOO - ,

C 2 O 4 2-, Cl - , SO 4 2-, NO 3

-

Cationic acids

NH 4 + and

Onium cations of amines, e.g. R-NH 3 + , R 2 -NH 2 + and R 3 -NH +

22

3- Lewis theory :

Acid : Is substance which accept lone pair of electrons

Base : Is substance which donate lone pair of electrons eg NH 3 , amines. contain atom with unshared-pair of electrons e.g., N,O,S,P

eg. BF 3 , AlCl 3 .

of electrons e.g., N,O,S,P eg. BF 3 , AlCl 3 . L . acid L .

L . acid

L . base

e.g., N,O,S,P eg. BF 3 , AlCl 3 . L . acid L . base Adduct

Adduct

Co- ordinate bond

Neutralization is the sharing of an electron pair between an acid and base and form

a coordinate covalent bond. This may be followed by ionization.

H + Cl - + :NH 3

may be followed by ionization. H + Cl - + :NH 3 NH 4 + Cl

NH 4 + Cl -

by ionization. H + Cl - + :NH 3 NH 4 + Cl - NH 4

NH 4 + +

According to Lewis theory, the presence of H

- Ammonia (NH 3 ) is a base although does not contain no OH -

- Borontrichloride is a Lewis acid although contain no H + atoms

+ or OH

- is not essential

Cl -

The Law of

Mass Action

The velocity of a chemical reaction is proportional to the product of the active masses {concentration in gram /mols} of the reacting substances

A+B

(f) (b)
(f)
(b)

C+D

The velocity of the forward reaction (f) depends on the concentration of both A and B, where;

V f [A] [B]

or

V f =

K f [A] [B]

K f is the velocity constant of the forward reaction, square brackets [ concentration.

V b =

K b [C][D]

]are used to denote the molar

K b is the velocity constant of the backward reaction (b).

At equilibrium, the velocities of the forward and backward reactions will be equal.

V f =

V b

K f [A][B] = K b [C][D]

K = K f / K b = [C][D] / [A][B]

= K b [C][D] K = K f / K b = [C][D] / [A][B] “

K = equilibrium constant at constant temperature."

9/22/2014

Acid - base Equilibrium In Water

When an acid or base is dissolved in water, it will dissociate, or ionize, the

amount of ionization being dependent on the strength of the acid or base.

A strong electrolyte is completely dissociated while

A weak electrolyte is partially dissociated,

Degree of Dissociation:

Molecules

is partially dissociated, Degree of Dissociation : Molecules Cations + Anions When an electrolyte is dissolved

Cations + Anions

When an electrolyte is dissolved in water, it dissociates into:

Positively charged fragments (cations) and

Negatively charged fragments (anions) Each ion have its specific reactions.

Degree

of

Dissociation: For each concentration is a state of a reversible equilibrium

between undissociated (unionized) molecules and ions.

between undissociated (unionized) molecules and ions. F or strong electrolyte, dissociation is complete F or weak

For strong electrolyte, dissociation is complete

For weak elecrolyte

= unity or nearly

far from unity

9/22/2014

Example The Degree Of Dissociation Of:

HCl H + + Cl - 0.92 HNO 3 H + +NO 3 - 0.92
HCl
H + + Cl -
0.92
HNO 3
H
+ +NO 3
-
0.92
CH 3 COOH
H + + CH 3 COO -
0.013
H
H + +H 2 BO 3
-
0.001
3 BO 3
NaOH
Na + +OH -
0.91
NH 4 OH
NH 4 + + OH -
0.013
NaCl
Na + + Cl
0.86
CH 3 COONa
Na + +CH 3 COO -
0.80
CuSO 4
Cu 2 +SO 4 2-
0.39
HgCl 2
Hg 2+ +2Cl -
0.01

HCl is a strong acid i.e. its ionization is complete

HCl

+

H 2 O

H 3 O +

+ Cl -

Acid - base Equilibrium In Water

The equilibrium, which exists in a dilute solution of an acid, like acetic acid (HAc) at constant temperature:

HAc

an acid, like acetic acid (HAc) at constant temperature: HAc Applying the law of mass action:

Applying the law of mass action:

H +

+

Ac -

HAc Applying the law of mass action: H + + Ac - "K" is the ionization

"K" is the ionization constant or dissociation constant of the acid, or acidity constant, usually written K a

Acid - base Equilibrium In Water

When a polybasic acid {An acid with more than one replaceable hydrogen atom}

dissolved in water, the various hydrogen atoms undergo ionization to different extents.

H 2 A HA - Applying the law of mass action:

H 2 A HA - Applying the law of mass action: H + + HA -
H 2 A HA - Applying the law of mass action: H + + HA -

H + + HA - H + + A 2-

[H + ] [HA - ] / [H 2 A] = K 1

K 2

[H + ] [A 2- ] / [HA - ] =

K 1 and K 2 are known as the primary and secondary dissociation constants, respectively.

The greater value of K 1 relative to K 2 the smaller be the secondary dissociation, and the greater must be the dilution before the letter becomes appreciable.

The stronger the acid the larger the acidity constant. For a completely ionised acid, the acidity constant is assumed to be =1

moderately Strong acid

A weak acid

Extremely weak acid

H 3 PO 4 H 2 PO 4 - HPO 4 2-

acid H 3 PO 4 H 2 PO 4 - HPO 4 2 - H 2
acid H 3 PO 4 H 2 PO 4 - HPO 4 2 - H 2
acid H 3 PO 4 H 2 PO 4 - HPO 4 2 - H 2

H 2 PO 4 - + H + HPO 4 2- + H +

PO 4 3- +

H +

(Ka 1 =1.1X10 -2 ) (Ka 2 =1.1X10 -7 ) (Ka 3 =3.6X10 -13 )

The Dissociation of Water

The dissociation of water is an endothermic process, it, therefore, increases with

temperature.

Applying the law of mass action:

H 2 O

with temperature. Applying the law of mass action: H 2 O H + + OH -

H + + OH -

Applying the law of mass action: H 2 O H + + OH - K w

K w is the ionic product of water and is = 1x10 -14

at 25 o C.

Since, water is weakly dissociated, the value of H 2 O is considered unity.

dissociated, the value of H 2 O is considered unity. The H + ion and OH

The H + ion and OH - ion concentrations are equal in pure water, i.e.,

[H + ] = [OH - ] = 1X10 -7

(at 25 o C)

o

A solution in which [H + ] =[OH - ] is said to be neutral.

o

A solution is said to be acidic when [H + ]>[OH - ];

o

It is basic when [OH - ] > [H + ]

9/22/2014

Acid-base titration in aq. medium

Solns. are classified into

Acid-base titration in aq. medium Solns. are classified into Electrolytes Which dissociate (ionize) and conduct

Electrolytes

Which dissociate (ionize) and

conduct electricity.

Dissociation of water

Non electrolytes

Which doesn't ionize and doesn't conduct electricity.

H 2 O

ionize and doesn't conduct electricity. H 2 O H + + OH - Dissociation const. Kw

H + + OH -

doesn't conduct electricity. H 2 O H + + OH - Dissociation const. Kw = [

Dissociation const. Kw = [ H + ] [OH - ] / [H 2 O]

- Since H 2 O is weakly dissociated , therefore H 2 O is considered unity.

therefore Kw = [H + ] [OH - ] = 10 -14

Kw : it is called ionic product of water. At 25 o c

If [H + ] = [OH - ] , therefore soln. is neutral

If [H + ] > 10 -7 eg 10 -6 , 10 -5 , therefore soln. is acidic

at 25 o c

[H + ] = [OH - ] = 10 -7

Hydrogen Ion Exponent “pH"

(at 25 o C)

pH

=

- log [H + ]

pOH = - log[OH - ]

[H + ] [OH - ]

=

K w =

10 -14

-log[H + ] + -log [OH - ]

= - log

K w =

pH

+

pOH = pK w = 14

The pH of pure water = - log 10 - 7 = 7.

In neutral solution the pH or pOH = 7.

- log 10 -14

- log = p

Acidic solution have pH values less than 7, while alkaline solutions have pH values greater than 7.

A pH increase of one unit corresponds to a tenfold decrease of [H + ].

pK w

=

pH +

pOH = 14

pH

= 14

-

pOH

9/22/2014

pOH

= 14

- pH

31

Hydrogen exponent : pH

- log = p

pH = - log 10 -7 = 7

pH = -log [H + ]

i.e. If [H + ] = 10 -7

In acidic side i.e. If [H + ] = 10 -6

In basic side i.e. If [H + ] = 10 -8

pH = - log 10 -6 = 6

pH = - log 10 -8 = 8

i.e. as pH value ↑ inc.

= 6 pH = - log 10 - 8 = 8 i.e. as pH value ↑

[H + ] conc. ↓ decrease.

Therefore

Alkaline soln. has pH more than 7

Acid soln has pH less than 7 ,

Neutral soln. has pH = p OH = 7

A pH increase of one unit corresponds to a tenfold decrease of [H + ].

pK w

=

pH +

pOH =

14

to a tenfold decrease of [H + ]. pK w = pH + pOH = 14

Example: If the

[H ] = 3

+

× 10

-8

pH = - log [H + ] = - log ( 3 × 10 -8 )

= - ( log 3 + log 10 -8 )

Calculate the pH ?

= - ( 0.4771

+

-8) = -

0.4771 + 8

=

7. 523

32

The pH scale

The pH scale ranges from 1 to 14.
The pH scale ranges from 1 to 14.

pH = - log [H 3 O + ] = - log [ H + ]

1

2

3

4

5

6

7 8 9 10 11 12 13 14

acid neutral base
acid
neutral
base

pH

of

pH of strong Acid :

Acids

and

Bases

Strong acids are assumed to be completely dissociated, i.e., the concentration of the acid = [H + ]

Therefore, for strong acids:

pH = pC a = - log [H + ]

where:

C a = conc. of the acid

if we have 1 M solution of HCl the [H + ] will be = 1 pH = - log 1 = 0

pH increase of one unit corresponds to a tenfold decrease of [H + ].

Calculate the pH of 0.1N HCl? 0.1N HCl gives [H + ]= 0.1

So,

pH = - log 0.1 = - log 10 -1 = 1

Calculate the pH of 0.01 M solution ? 0.01N HCl gives [H + ]= 0.01

So,

pH = - log 0.01 = - log 10 -2 =

2

9/22/2014

pH

of

Acids

and

Bases

pH of Strong Bases:

Strong bases are assumed to be completely dissociated, i.e., the concentration of the base = [OH - ]

i.e., the concentration of the base = [OH - ] ? Therefore, for strong base: pOH

?

Therefore, for strong base:

pOH = pC b = -log [OH - ]

? ? ?
?
?
?

where:

C b = conc. of the base

pK w

Calculate the pH of 0.1 N NaOH? pOH = pC b = - log [OH] = - log 0.1

- log 10 -1 = 1

=

= pH

+

pOH

=

14

pH

= pK w pOH

pH

= 14 pOH

= 14 1 = 13

Calculate the pH of 0.01 N NaOH? pOH = - log [OH] = - log 0.01

So,

pOH =

- log 10 -2 =

2

pH = 14 pOH

= 14 2 = 12

9/22/2014

pH of Weak Acids:

Most of the weak acid is present in the form of almost undissociated

molecules, only a small portion is dissociated with formation of H + ions.

HAc

portion is dissociated with formation of H + ions. HAc H + + Ac - pH

H + + Ac -

pH =

½

pC a + ½ pK a

=

½

(pC a +

pK a )

Where K a is dissociation constant of the acid

pH

of

Weak

Bases :

BOH

is dissociation constant of the acid pH of Weak Bases : BOH pK w = pH

pK w = pH

+

pOH

pH

= pK w -

pOH

B + +OH -

pOH = ½ pC b + ½ pK b = ½ ( pC b + pK b )

pH = pK w - (½ pC b

+

½ pK b )

=

pK w -

½ ( pC b

+

pK b )

Where, C b is the total concentration of the base K b is the dissociation constant of the weak base.

9/22/2014

pH of Salt Solutions

1- Salts of strong acid and strong bases:

e.g., KCl, NaCl, The solution of such salts are neutral (pH 7).

2- Salts of strong acids and weak bases:

e.g., NH 4 Cl, the solution is acidic (pH 7).

pH = ½pK w - ½pK b + ½pC s =

½

(pK w -

pK b +

pC s )

C s = conc. of the salt

K b = dissociation constant of weak base

3-

e.g., sodium acetate, the solution is alkaline (pH 7):

Salts of

weak acids and strong bases:

pH

=

½pK w

+

½pK a

-

½pC s

=

½ ( pK w +

pK a -

pC s )

C s = conc. of the salt

K a = dissociation constant of weak acid

4- Salts of weak acids and weak bases:

e.g., ammonium acetate

pH

=

½ pK w + ½ pK a -

½ pK b

=

½ ( pK w +

pK a -

pK b )

9/22/2014

pH of acid and bases :-

1- pH of strong acids :-

2- pH of strong bases :-

Since strong acids are strongly ionized.

strong bases are completely ionized.

 

Therfore pH = pCa

(Ca is conc. of acid)

So pOH = p Cb (Cb is conc. of base)

 

pH = -log [H+]

 

pH = p Kw p OH

 

pH = -log pCa

 

i.e. pH = p Kw p Cb.

i.e. 0.1 N HCl

pH = - log 0.1= - log 10-1 = 1

i.e. 0.1 N NaOH pH = 14 _ 1 = 13

 

3- pH of W acids :

 

4- pH of W bases :

 
 

pH = 1/2 pCa + 1/2 pKa

   

pH =pKw - 1/2 pCb - 1/2 pKb

 

5- Salts

of

S

A

&

W

B:

6- Salts

of

W

A

&

S

B:

 

e.g., NH 4 Cl, solution is acidic (pH 7). pH = ½pK w - ½pK b + ½pC s

 

e.g. sodium acetate

pH

=

½pK w

½ ( pK w +

=

+

pK a -

½pK a pC s )

-

½pC s

=

½

(pK w -

pK b +

pC s )

   

6- Salts

of

S

A

&

S

B:

8- Salts

of

W

A

&

W

B:

e.g., KCl, NaCl, The solution of such salts

   

are neutral (pH 7).

 

pH

e.g., ammonium acetate =

½ pK w + ½ pK a -

½ pK b

 

=

½ ( pK w +

pK a -

pK b )

BUFFER

SOLUTIONS

BUFFER SOLUTIONS

Buffer

Solution solutions, which resist changes in the pH, upon addition of

small amounts of strong acids or base. This resistance to the change in the H

buffer action. A buffer contains both: An acidic species (to neutralize OH ) and a basic species (to neutralize H + ).

+ conc. is called

Types of buffers

neutralize H + ). + conc. is called Types of buffers + W acid + its
+ W acid + its salt acetic acid CH 3 COOH sodium acetate CH 3
+
+

W acid + its salt

acetic acid CH 3 COOH sodium acetate CH 3 COONa

acetic acid CH 3 COOH sodium acetate CH 3 COONa pH = pk a + log

pH = pk a + log [Salt] / [Acid]

+
+

pH

=

W base + its salt

pK w - pK b

pK w - pK b

Henderson equation for acidic buffer

ammonium hydroxide NH 4 OH ammonium chloride NH 4 Cl

- log [Salt] / [Base]

40

How can buffers resist pH changes ??? How we can calculate pH of buffers???

1- Type I: weak acid & its salt: HAc and NaAc Upon the addition of a strong acid: as HCl The strong acid is, therefore converted to a weakly dissociated acid and the pH practically dose not change.

H + + NaAc

acid and the pH practically dose not change. H + + NaAc HAc (weak acid) +

HAc (weak acid) + Na +

Upon the addition of a strong base: NaOH The alkalinity, converted from a freely ionized OH - to water.

OH - + HAc

from a freely ionized OH - to water. OH - + HAc H 2 O +

H 2 O + Ac - (salt)

The pH of this buffer is calculated from eq.,

pH = pk a + log [Salt] / [Acid]

Henderson equation for acidic buffer

- Maximum buffer capacity obtain when ratio of acid to salt = 1

i.e.

pK a = pH

obtain when ratio of acid to salt = 1 i.e. pK a = pH 41 -

41

- Adequate buffer capacity obtained when pH= pKa 1

i.e salt/ acid =10/1 or 1/10

pH =

pk a + log 10/ 1 =

pK a

+ 1

pH =

pk a + log 1/ 10 =

pK a

-

1

How can buffers resist pH changes ???

How we can calculate pH of buffers???

2- Type 2: Buffers from weak bases and their salts: e.g., NH 4 OH / NH 4 Cl

o

Upon the addition of an acid:

 

H +

+

NH 4 OH

It converts acid into water NH 4 + + H 2 O

+ NH 4 OH It converts acid into water NH 4 + + H 2 O

o

Upon the addition of a base: It convert base into NH 4 OH

 

OH - +

NH 4 Cl

NH 4 Cl NH 4 OH + Cl -

NH 4 OH + Cl -

pH

=

pK w - pK b

- log [Salt] / [Base]

Henderson equation for basic buffer

The ratio [Salt] / [Acid, base]

Buffers of different pH values are prepared by varying the buffer ratio.

is known as Buffer ratio.

Buffer capacity :

Is the resistance of a buffer to pH changes upon the

addition of a strong acid or base.

The higher buffer capacity the more efficient the buffer.

9/22/2014

Examples: Calculate the pH of an acidic buffer solution contain 0.1M HAc and 0.01M NaAc (K a = 10 -5 ) ?

pH = pk a pH

+ log [ salt ]/ [ acid

-1 = 4

= 5

= - log 10 -5

+ log

10 -2 / 10 -1

Examples: Calculate the pH of a basic buffer solution contain 0.01M NH 4 OH and 0.1M NH 4 Cl (pK b = 4.76) ?

pH = pk w

- pk b -

= 14 4.76

log [ salt ]/ [ base]

log 10 -1 / 10 -2

pH = 8.24

- 1

= 7.24

Calculate the pH of a buffer solution containing 0.1M sodium acetate and 0.1 M acetic acid (pK a = 4.76).

Calculate the pH of a solution containing 0.07 M ammonia and 0.28 M ammonium chloride (pK b = 4.76).

N.B:

log 10 = 1

log 1/10 = -1

log 1= 0

9/22/2014

Neutralization

Indicators

o

Neutralization reactions are not accompanied by visible changes of the color of the solution.

o

A suitable indicator must be added during titration in order to determine the equivalence

point.

Color Indicator :

Are organic dye, the presence of very small amount of it indicates the termination of a

chemical reaction by a change of colors,

Neutralization indicators, e.g., methyl orange (M.O) and phenolphthalein (ph. Ph.) change

color with change of pH of the medium.

Theories of Color Indicator:

1- Ostwald Arhenious Theory of Indicator:

Ostwald considered neutralization indicator to be either weak organic acids or bases, and partially dissociate in aqueous solution, in which undissociated molecules differ in color from their ions.

Acidic indicators., e.g., phph

H Ind

from their ions. Acidic indicators., e.g., phph H Ind H + + Ind - “pink” (in

H + + Ind - “pink”

(in acidic medium) "Colorless"

(in basic medium)

Basic indicators., e.g., M.O

 

Ind OH

Ind + + OH -

Ind + + OH -

(in basic medium)

"Yellow"

"Red”

(in acidic medium)

9/22/2014

Neutralization

Indicators

Certain objection had been raised against theory of Ostwald:

When a small quantity of alkali is added to ph. ph. solution it turns red, but addition of more alkali a colorless solution, while according to the theory, the color should

increase.

2- Chromophoric Theory The color change of indicators is due to the presence of unsaturated groups called chromophores. As nitro N = O 2 , nitroso N = O, azo N = N, or double bond conjugated C=C-C=C.

The color of organic compounds is also influenced by the presence of another type of groups known as auxochromes

with

Auxochromes

together

chromophores they increase the action of the it and deepen the color produced by them.

cause auxochromes are

and

can

not

give

color

to

a

compound

but

when

present

The

Auxochromes

a -OH and NH 2 groups.

bathochromic

hyperchromic

effect.

most

important

The color change of an indicator is the result of an isomeric change, i.e., an intramolecular

rearrangement which changes the structure of the indicator.

9/22/2014

Benzenoid Free phph, colorless at pH 7 No charges Quinonoid (chromophore) Resonance hybrid, red at
Benzenoid
Free phph, colorless at pH 7
No charges
Quinonoid (chromophore)
Resonance hybrid, red at pH 8-10
2 -ve charges
Tribasic salt
3 -ve charges
No chromophore, colorless at pH > 12
Increasing pH

46

Neutralization Titration Curves

The titration curve is a plot of pH versus the volume of