trimetric Analysis Neutralization Reactions

Neutralization Reactions

• Are chemical processes in which an acid (proton donor)

reacts with a base (proton acceptor)

• Products of neutralization reaction in an aqueous

solution are water and salt, depending upon the acid or

base used in the reaction

- Chemical processes in which an acid reacts with abase

- The products of neutralization reaction in aqueoussolution are

water and salt.

• SA and SB

• SA and WB

• SB and WA

Titration Curves

• Shows the change of pH of solution during a titration’

Titration Curves

•Equivalence point – portion in the titration curve where

the slope of the curve is steepest (break)

• *When an indicator is used to detect the equivalence

point in the titration, it must give a sharp discernible

color change at that point in the titration

Preparation of Titration Curves

1. pH of the solution being titrated but before any titrant is

added

2. 2. pH of the solution after titrant is added but before the

equivalence point is reached

3. 3. pH at the equivalence point

4. 4. pH beyond the equivalence point

Example

• Titration of 50mL of 0.2 M acetic acid, qs water to make

100mL, against 0.05 M sodium hydroxide

1. Calculate pH of solution before any titrant is added

2. Calculate pH of solution after 100 mL of 0.05 M sodium

hydroxide

Titration Curves

Acidimetry

• Titrimetric analysis of bases using an accurately measured

volume of acid

Direct Titration

• Conducted by introducing a standard acid solution

gradually from a buret into a solution of the base being

assayed until chemically equivalent amounts of each have

reacted

• NaHCO3

, NaOH, Na salicylate, Na benzoate

Residual Titration or Back Titration

• Used when a reaction proceeds slowly or when the

substance to be assayed does not give a distinct , sharp

endpoint with an indicator by direct titration

• Carried out by dissolving the substance in an accurately

measured quantity of standard solution (in excess) and

titrating the excess with another standard solution

Residual Titration or Back Titration

Examples:

• ZnO (slow dissolution ) – add NH4Cl, heat

• C4H4KNaO6, and other alkali salts of citric, tartaric, etc

• MgO,Mg(OH)2

• Methenamine

Alkalimetry

• Titrimetric analysis of acids using an accurately measured

volume of bases

• Most inorganic acids, MR or PH can be used, though the

alkali should be standardized with a particular indicator

used

Alkalimetry

• For organic acids, PH is freq used; though thymol blue,

bromothymol blue, thymolphthalein are also used

Direct Titration

• HCl, Dil H3PO4,H3BO3,

• Determination of Hydroxy Compounds by

Esterification with Acetic Anhydride

• Blank determination isrequired

Residual Titration

• Esters, acid anhydrides, acid chlorides, aldehydes

• Aspirin,Formaldehyde

Non-aqueous Titrimetric Analysis

• To overcome poor solubility and weak reactivity from

aqueous titrations

• Moisture is to be avoided in using nonaqueous

procedures (less than 0.05% moisture)

Non-aqueous Titrimetric Analysis’

• Water will compete with the weak nitrogen base for the

HClO4

• H2O + HClO4 → H3O+ + ClO4-

• RNH2 + HClO4 → RNH3+ + ClO4-

• *Sharpness of endpoint will belost

Non-aqueous Titrimetric Analysis

• Control of temperature → organic solvents havehigher

coefficients of expansion

• Neutralization – reaction b/n weakly protophyllic

substances which tend to accept a pair of electrons and

highly protophyllic substances which tend to provide a

pair of electrons in the formation of covalent bonds by

coordination

• End point

• Indicator is chosen which will give the sharpest color

change for the least increment of volume of titrant added

near the equivalence point

• Titration od weakly basic substances in glacial acetic acid

(amines, amine salts, heterocyclic nitrogen compounds,

alkali salts of organic acids, alkali sats of weak inorganic

acids, and amino acids) using perchloric acid

• Solvents:

• Neutral solvents (acetonitrile, alcohol, chloroform,

benzene, dioxane, or ethyl acetate) – either aprotic or

amphiprotic, do not enhance dissociation to any degree

• Solvents:

• Acidic solvents (formic, glacial acetic, propionic acids,

acetic anhydride, and sulfonyl chloride) – used for weak

bases and their salts where protogenic quality of solvent

is utilized

Titrant:

• Perchloric acid in glacial acetic acid

• Dioxane

• Hydrogenbromide’

Non-aqueous Acidimetry

Indicators

• Titration of weak bases and their salts – crystal violet,

methylrosaniline chloride, quinaldine red, anaphtholbenzein, malachite green

• Titration of strong bases – MR, MO, thymol blue

Non-aqueous Alkalimetry
• Compounds to be titrated: acid halides, anhydrides,

acids, amino acids, enols (barbiturates, xanthines,

imides, phenols, pyrroles, sulfonamides, and organic

salts of inorganic acids)

Solvents

•For enols – ethylenediamine, n-butylamine,

morpholine

• For medium-strength acids – dimethylformamide,

pyridine

Titrants

• Sodiummethoxide

• Lithiummethoxide

• Sodiumaminomethoxide

• Sodiumtriphenylmethane

Non-aqueous Alkalimetry

•Indicators

•Azo violet

•O-nitroaniline

• Thymolphthalein

•p-hydroxyazobenzene’
Solvents

✓Protogenic solvent – proton giving

✓Protophilic solvent – proton receiving

Aprotic solvent – neither

(Benzene)
Titrimetric Analysis Precipitation

Precipitation Method

• Require the formation of relatively insoluble substances

or precipitates to cause the reactions to go to sufficient

completion

• Based upon reactions that yield ionic compounds of

limited solubility

• Analyte is titrated with a standard solution of a precipitating

agent in accordance with defined reaction stoichiometry

• Detection of the end point (at completion of the

precipitation) is usually either the appearance of excess

titrant or the disappearance of the reactant

Requirements for Precipitation Method

1. The precipitate formation is stoichiometric

2. To allow the titrant to be added quickly, the equilibrium

between the precipitate and its ions in solution must be

attained rapidly

3. The precipitate must be of low solubility in the solution

4.A method to detect the stoichiometric point of the

titration must be available

Solubility Product Principle

• In a saturated solution of a difficulty soluble electrolyte ,

the product of the formal concentrations of the ions, each

ion raised to the power equal to the number of timesit

occurs in the formula, is a constant at a given temperature’

Solubility Product Constant (Ksp)

• Are used to describe saturated solutions of ionic

compounds of relatively low solubility

Relationship of Solubility Product to Solubility

• The numerical values of solubility products cannot be

compared in relation to the solubility of the salts

• Numerical value of the Ksp depends upon the conc of ions

produced by the relatively insoluble salt

• Very small Ksp ~ very insoluble

• E.g.

Ag2

S – Ksp 1.6 x 10-49

AgC2H3O2 – Ksp 1.8 x 10-3

Calculation of Ksp from Solubility

• Calculate the solubility of SrC2O4

in GFW/L and in g/L if

Ksp is 1.4 x 10-7? FW 176

• The solubility of AgI is 2.9 x 10-6/L. Calculate the Ksp.

Ksp and other factors

• Temperature – different temp will have diff Ksp

• Common ion – small amounts of common ion can alter

equilibrium

• Salt – decrease rate of precipitation

Methods in Precipitation Methods

Argentometric Methods

• Titration methods based upon utilizing silver nitrate as

a precipitating agent

• Silver ion is extremely useful in precipitation reactions

including:

• Halides (Cl-, Br-, I-)

• Pseudohalides (S2-, HS-, CN-, SCN-)

• High reagent conc give sharper, more dramatic equivalence

point changes in pAg

• The smaller the Ksp, the more complete the precipitation

reaction and the sharper the equivalence region changes

• Both Ksp and the reagent conc affect the choice and use of

an endpoint indicator
’

EndpointIndicators for Argentometric

Titrations

• Indicators for argentometric titrations are selected to

produce color change at or near the equiv point

• Normally the indicator is selected to react with the added

titrating agent, not the analyte

• The smaller the excess added to cause the color change,

the smaller the endpoint error

• The indicator should give large color changes at very low

Concentrations
3 Classical Methods

Mohr • Formation of colored ppt at endpoint

Volhard • Formation of soluble, colored complex at endpoint

Fajans • Adsorption of colored indicator on the ppt at endpoint

Mohr Method

• Was first published in 1855 as method

for chloride analysis

• Potassium chromate is used as an

indicator

• Formation of silver chromate (reddishbrown)

• Suitable only for Cl-, Br-, and CN

• The titration is performed only in neutral or slightly basic

pH

• if pH > 10 formation of AgOH

• If ph < 7 formation of chromic acid’

• Errors are introduced due to the need to add excess titrant

before the endpoint color is visible

• To overcome this, it is necessary to carry out blank titrations

• It is also important to use a constant amount (1mL) of

indicator in all titrations

Why?

1. If too little indicator, silver conc must be higher after

equiv point before any ppt of Ag2CrO4 occurs

2. If too much indicator is used, the color change will be

difficult to see due to the intense yellow color

• Other limitations

1. Cations give insoluble chromate e.g. barium ions ~ must be

absent or removed before titration

2. Reverse titration of Ag+ with Cl- using CrO4-2 is not

feasible

3. Titration of iodide and thiocyanate is not successful, AgI

and AgSCN adsorb chromate ions

4. Late equivalence point

Volumetric Solution AgNO3, VS

Indicator Potassium Chromate
Primary Standard Sodium Chloride
Manifestation Red Precipitate of Ag Chromate
Assay of Sodium Lauryl Sulfate for NaCl content

Volhard Method

• Determination of Cl-, Br-, I- in acidic solutions

• Back titration with potassium thiocyanate

• A known excess of AgNO3 sol is added to the sample and the

excess is back titrated with standard SCN sol

• Uses the ferric ion as indicator

• The solution must be acidic, with a conc of about 1M in nitric

to ensure the complex formed is stable and prevent ppt of

iron hydroxides

• Method is suitable for the direct determination of silver ion

or for the indirect determination of halide ions

• Error is introduced in the method for the analysis of chloride

as AgCl is more soluble than AgSCN (some of the AgCl ppt

will redissolve by reacting with SCN titrant)

• Can be overcome by:

• Filtering off the ppt prior to titration à transfer error

• Adding nitrobenzene which forms an impervious coating on

the AgCl ppt preventing it reacting with the SCN-

• SCN is standardized against a std AgNO3 sol, with the Ag sol

in the titration flask and the SCN in the burette’

Volhard Method – Advantages

• Acidic environment gives advantage for halide analysis

because anions (carbonates, oxalate and arsenate) do not

form precipitate

• Gives an accurate result due to the back titration’

Volhard Method – Disadvantages

• Cannot be used in neutral or alkaline medium

• Time consuming

Volumetric Solution Ammonium Thiocyanate

Indicator Ferric Ammonium Sulfate aka: Ferric alum
Primary Standard AgNO3
Manifestation Red Color (Fe+3 thiocyanate complex)
Assay of Sodium chloride
Aminophylline
Fajans Method

• Uses an adsorption indicator such as fluorescein and eosin

• The indicator adsorb onto the surface of the silver salt ppt

at the endpoint

• The adsorption process causes a change in color of the

Indicator

• Common adsorption indicators are weakly acidic organic

compounds and in alkaline conditions will exist asthe conjugate

base, In

• AgNO3 added to dilute solution of NaCl, the solution becomes

turbid and if other electrolytes are absent, coagulation does not

occur immediately

• The colloidal sized AgCl particles adsorb Cl- and these attract

sodium ions

• Colloidal particles are electrically charged and repel each other

preventing coagulation

• As titration continues, the amount of Cl- decreases but

there is still some surface charge which acts to repel the

negatively charged indicator ion

• Immediately after endpoint there is an excess silver ions

which will adsorb onto the surface of the ppt

• The charged surface has now changed polarity and attracts

the negative indicator ion

• A color change will be observed

• A blank titration is not required as the indicator does not

react with the titrant

Limitations:

1. Low background levels of non-reacting ions to ensure that

coagulation does not occur

2. Will not work with very low levels as there will not be
enough ppt to allow the color change to be observed

3. Method is pH dependent as the indicator must be in

ionized form (slightly alkaline)’

• Conditions that favor the formation of colloids:

1. Fast addition of reagents

2. Add dextrin to retard coagulation

3. pH control is important to generate the dye anion in

solution

4. Avoid light – Ag-dye complex is light sensitive and

decomposes after a while

• Can be used to titrate silver with a standard chloride

solution

• This is not possible in Mohr’ since chromate added to silver

sol would immediately cause a precipitate

• Common adsorption indicators

\\

Indicators - Fluorescein

• Can be used during the titration of halides

• Very weak acid ~ small amount of other acids reduces

ionization ~ impossible or difficult to observe

• Optimum pH 7 to 10
Indicators – Dichlorofluorescein

• Stronger acid and may be utilized in slightly acid solution of

pH greater than 4.4

• Applicable in very dilute solutions

Indicators – Eosin

• Aka tetrabromofluorescein

• Stronger acid; can be used down to a pH of 1.2

• Color change is sharpest in HAc

Volumetric Solution AgNO3, VS

Indicator Adsorption indicators/Fajan’s
Primary Standard Indicator
Manifestation NaCl
Change in the color of the
silver halide precipitate
Gay Lussac Method

• Titration of Cl- requires sufficient time between the addition

of Ag to allow the ppt. to settle.

• Titration is continued until such time further addition of

reagent fail to produce turbidity

Volumetric Solution AgNO3, VS

Indicator None
Primary Standard NaCl
Manifestation Cessation of precipitate
Assay NaCl

Turbidity Method

• Appearance of turbidity ~ end point

Liebig Method:

• When a solution of AgNO3 is added to a solution containing cyanide

ions (e.g. alkali cyanide), a white ppt is formed ~ re-dissolves upon

stirring

• When the reaction is complete, further addition of AgNO3

solution yields insoluble silver argento cyanide

Denige’s Modification

• Iodide ion is used as indicator and aqueous ammonia is introduced

to solubilize the silver cyanide

Denige’s Modification

• Iodide ion and ammonia solution are added before the

titration is commenced, the formation of AgI (as turbidity)

will indicate the end point

Denige’s Modification

• During the titration, any AgI will be kept in solution by the

excess of cyanide ion always present until the equivalence

point is reached

]]

Denige’s Modification

• Can be utilized indirectly for the determination of several

metals – Ni, Co, Zn ~ form stable stoichiometric complexes

with CN’
Limitations of Argentometric Titration

1. Reducing agents (e.g. SO2) interfere by reducing Ag+,

and must be removed by previous oxidation

2. Colored compounds of any sort obscure the endpoint

3. Silver halides are sensitive to photodecomposition,

titration should be carried out in diffused daylight or

artificial light
4.Most cations except the alkalies and alkaline earths

interfere in several ways

• Fe+3 form insoluble colored hydroxidesin neutral or slightly

acid medium

• Al+3 hydrolyze to insoluble basic salts in neutral orslightly

acid solution

• Hg+2 form sol complexeswith halides

5.A few number of ions such as halide ions can be titrated by

precipitation method

6. Co-precipitation may occur

7. Difficult to detect end point

Computations

Indirect purity=

(mEq AgNO3- mEqSCN)X mEq sample X 100

Weight of sample

(mL X N)-(mL X N) X mEq sample X 100

Weight of sample

Direct purity=

(mEq AgNO3- mEqSCN)X mEq sample X 100

Weight of sample

mL SCN X N SCN X mEq sample X 100

Weight of sample
Precipitation Method

Types of drug that can be analyzed by this method:

• Carbromal

• KCl infusion

• NaCl infusion

• Thiamine HCl

Other applications of precipitimetry

1. Determination of Zn ions by precipitation with

K4Fe(CN)6 using external indicators uranyl nitrate and

ammonium molybdate; end point: light brown color

2. Determination of Ba+2 and SO4-2

2. Determination of Ba+2 and SO4-2

• Solubility of red compound is much greater than that of

BaSO4 ~ upon addition of SO4 solution, the barium will be

completely precipitated when the red color changes to

colorless (in weak acid solution) or yellow (in neutral solution)

3. Determination of Mixtures

Mixture Method
Chloride-iodide By direct titration using Fajan’s method
(fluorescin for total halide, eosin for iodide)
Bromide-iodide Same method

Chloride-cyanide, bromide cyanide, or iodide- Liebig’s (CN- only) and Volhard’s (total
cyanide