Nickel ion is precipitated with a very selective organic

precipitating reagent called dimethylglyoxime (DMGH) and then adding a slight excess of aqueous ammonia solution.

Determination of Nickel

Determination of Carbon and Hydrogen

Determinations are based on direct volatilization

procedure and require only 5 to 10 mg of sample The sample is heated in a steam of oxygen in the presence of catalysts, causing it to decompose into CO2 and H2O C10H8 + 12 O2 10 CO2 + 4 H2O

Volumetric method of analysis

Titration
process

wherein a stoichiometrically equivalent quantity of a standard solution is systematically added to a known quantity of a sample

Requirements of a Titration:
Stoichiometric

Reaction must

be rapid No side reactions Presence of marked change in solution when the reaction becomes complete quantitative

Equivalence
point

point

in which the amount of standard titrant added is chemically equivalent to the amount of the analyte in the sample of equivalence point manifested by a change in physical properties of solution

Endpoint
estimation

Titration

error

Difference

between equivalence point and endpoint; minimized by:

Using a suitable

indicator Using an indicator blank

Standard
solution

solution
of known concentration

standardization
Process

of determining the concentration of a solution of unknown concentration

Common Acid-Base Indicators

pKln Methyl Orange Methyl Red Bromcresol Green 3.46 5.00 4.66 Acid/Base Colors Red/yellow Red/yellow Yellow/blue

Bromthymol 7.10 Yellow/blue Most Suitable Indicator: the one with pKln closest to the Blue pH at equivalence point 9.0 Phenolphthalein Colorless/red Methyl Violet 1.6 Yellow/violet

Strong Acids HCl HNO3 H2SO4 HClO4 HBr HI

Strong Bases NaOH KOH Ba(OH)2 CH3NOH C2H5NOH

Dissociation Constant, Ka/Kb

When

a weak acid or weak base is dissolved in water, partial dissociation occurs HA + H2O H3O+ + A HA = weak acid; Ka = acid dissociation

Ka = [H3O+] [A-]/ [HA] For weak base, Kb = base dissociation constant B + H2O BH+ + OH-

 Multiplication

of one equilibrium-constant expression by the other gives Ka x Kb = [H3O+] [A-]/ [HA] x [HA] [OH-]/ [A-] Ka x Kb = [H3O+] [OH-] Ka x Kb = Kw = 1.0 x 10-14 at 25C

pH Calculation
pH = - log [H3O+] When an acid HA dissolves in water, both acid and water are suppliers of H3O+: HA + H2O H3O+ + A(a) H2O + H2O H3O+ + OH(b) When a base B dissolves in water, both the base and water are suppliers of OH-: B + H2O BH+ + OH(c) H2O + H2O H3O+ + OH(d)

For Acids Case 1. The acid is the major supplier of H3O+

This means that the determination of hydronium ion concentration is based on the equilibrium expression for reaction (a) The hydronium ion concentration can be determined by solving the equilibrium expression for reaction (b) Both reactions must be considered

Case 2. Water is the major supplier of H3O+

Case 3. Both the acid and the water are major suppliers of H3O+

For Bases Case 1. The base is the major supplier of OH

This means that the determination of hydroxide ion concentration is based on the equilibrium expression for reaction (c) The hydroxide ion concentration can be determined by solving the equilibrium expression for reaction (d) Both reactions (c) and (d) must be considered

Case 2. Water is the major supplier of OH

Case 3. Both the base and the water are major suppliers of OH

Case 1 2 3

Major Supplier of H3O+ Strong acid Water Both

Necessary condition CHX >> 10-7 CHX << 10-7 CHX = 10-7

For acids Case 1. The acid is the major supplier of H3O+. [H3O+] = CHX Case 2. The water is the major supplier of H3O+.
[H3O+] = Kw Case 3. Both acid and water are the major supplier of H3O+. [H3O+] - CHX [H3O+] - Kw = 0

Case Major Supplier of OHNecessary condition 1 Strong base CB >> 10-7 2 Water CB << 10-7 3 Both CB = 10-7 For bases Case 1. The base is the major supplier of OH[OH-] = CB Case 2. The water is the major supplier of OH-. [OH-] = Kw Case 3. Both acid and water is the major supplier of OH-. [OH-]- CB [OH-] - Kw = 0 To solve for pH, use the equation below pH + pOH = pKw where pOH = - log [OH-]

For weak acids: Case Major Supplier of H3O+ 1 Weak acid 2 Water 3 Both Case 1. The weak acid is the major supplier of the H3O+. [H3O+]2 + Ka[H3O+] - KaCHA = 0 If CHA/Ka 10-3, [H3O+] = Ka CHA Necessary condition Ka x CHA >> 10-7 Ka x CHA << 10-7 Ka x CHA = 10-7

For weak bases o techniques used on weak acids are the same ones that are used to calculate hydroxide ion concentration in solutions of weak bases. Case Major Supplier of OHNecessary condition 1 Weak base Ka x CHA >> 10-7 2 Water Ka x CHA << 10-7 3 Both Ka x CHA = 10-7 o Case 1. The weak base is the major supplier of the OH-. [OH-]2 + Kb[OH-] KbCB = 0 If CB/Kb 10-3, [OH-] = Kb CB

Calculation of pH of conjugate acid-base pairs o There are two equilibria involved: HA + H2O H3O+ + A(e) A + H2O HA + OH (f ) + o The ionization of water is neglected, and [H3O ] is taken from reaction (e) Ka = [H3O+][A-] [HA] Where: [HA] = CHA - [H3O+] + [OH-] [A-] = CNaA + [H3O+] - [OH-] Ka =[H3O+]( CNaA + [H3O+] - [OH-]) CHA - [H3O+] + [OH-] Solving for [H3O+], [H3O+]3 + (CNaA + Ka) [H3O+]2 - (KaCHA + Kw) [H3O+] - KaKw = 0 o If CHA & CNaA 10-3 and Ka & Kb 10-3, then CHA and CNaA are larger compared to the difference between [H3O+] and [OH-], therefore [HA] = CHA [A-] = CNaA Ka becomes, Ka =[H3O+]CNaA CHA Note also that conjugate acid-base do not react with each other

pH buffers - a mixture of weak acid or base and its conjugate - resists changes in pH upon dilution or addition of acids or base o effect of dilution: pH = pKa - log [HA]/[A-] pH depends on the ratio of the concentrations of acids and conjugate bases rather than their absolute value

Buffer Capacity, - depends on both the concentration of components and the concentration ratio - Defined as the quantity of strong acid or strong base needed to cause 1.0 L of buffer to undergo a pH change of 1.0 unit - To determine the useful pH range of a buffer use the previous equation [HA] / [A-] pH from the equation 1 / 10 pHmax = pKa - log 1/10 = pKa + 1 10 / 1 pH min = pKa - log 10/1 = pKa - 1 Therefore the useful pH range is pKa 1. - In selecting a buffer for a given application there are two considerations to be considered: 1. The desired pH and 2. The chemical compatibility of the buffer components with the sample - Preparing a buffer: o By combining the calculated quantities of an acid-base conjugate pair o In cases one of the conjugate pair is unavailable, combining of excess of the available weak acid or baser with an appropriate amount of strong base or acid can be done. o Preparation of buffers uses the aid of pH meter

Polyprotic Acids and Polyequivalent Bases

Case 1: A solution containing H2A. The

stepwise ionization of

H2A provides two sources of H3O+:

H2A + H2O H3O+ + HA-

HA- + H2O H3O+ + A2

Ka1=[H3O+][HA-] [H2A] Ka2=[H3O+][A2-] [HA-]

if Ka1>>Ka2 and Ka1/Ka2 100, the first ionization is the major source of H3O+ ;the second ionization can be neglected for the purpose of calculating the pH

 Case 2: A solution containing H2A

+ HA-.

Similar to case 1: if Ka1/Ka2 100, the second ionization can be neglected and it becomes one of calculating the pH of a weak acid in the presence of its conjugate base--- a buffer problem Substances such as HA- exhibit both acidic and basic character. When a salt NaHA is dissolved in water, it dissociates completely into Na+ and HA-. The HA- can undergo ionization,

Case 3: A solution containing HA-.

HA- + H2O H3O+ + A2- And base ionization HA- + H2O H2A + OH-

Ka2=[H3O+] [A2-] [HA-]

Kb2=[H2A][OH-]= Kw [HA-] Ka1

 For case three both reactions should be considered,

[H3O+] = [H3O+]formed [H3O+]lost But [H3O+]formed = [A2-] and [H3O+]lost = [OH-]formed = [H2A] Therefore [H3O+] = [A2-] [H2A] Or [A2-] = [H3O+] + [H2A] Solving for Ka1, [A2-] = [H3O+] + [H3O+][HA-]/Ka1 We obtain Ka2 = [H3O+]([H3O+]+[H3O+][HA-]/Ka1) [HA-] [H3O+]2 = Ka1Ka2[HA] Ka1 + [HA-] It is frequent that Ka1 << [HA-] [H3O+] = Ka1Ka2

Calculation of pH of solutions of Salts

Salts of strong acid and strong base(ex NaCl)

pH = 7.0

salts of weak acid and strong base or salts of weak base and strong acid (ex. NaCH3COO;NH4Cl)

Reverse given dissociation constant

salts of weak acid and weak base (ex. NH4HCOO)

[H3O+] = KwKa/Kb

Concept of Equivalence

Equivalents (n)

Number of reacting species per mole of the species For acids and bases = replaceable H+ or OHFor ions = electrons that can be added or removed Redox reactions = electrons lost or gained

equation of equivalence
Between two aqueous solution NV = NV where N=M(n) between an aqueous solution and solid NV = weight solid/EW; EW = formula mass/n

DOUBLE-INDICATOR TITRATION
C:\Users\raissa\Documents\Neutralization

Titration.docx

DILUTION FACTOR
Simple dilution

DF = final volume/vol of aliquot added serial dilution final dilution factor = DF1*DF2*DF3

Complexometry

A titrimetric determination which involves the formation of a soluble but slightly dissociated complex or complex ion Metal ion + ligand complex (analyte) (chelate)

metal ion

central atom in the complex; lewis acid electron pair acceptor Group attached to the central atom; lewis base; can either be an anion or neutral molecule Metal ligand Well known complex

Ligand Complex

EDTA

 Coordinate number

The number of bonds formed by the central atom

Type of bonding involved in the metal-ligand complex

coordinate covalent bond

Titration of metals with polydentate ligands

Polydentate ligands and metals often react in a single step thereby avoiding the complications of stepwise reactions Indicators for EDTA titrations:

Eriochrome black T (EBT)

Used exclusively in the pH range 7-11 where the blue form of the indicator predominates in the absence of metal ions Endpoint: red to blue

Calmagite
Stable in aqueous solution; From red to orange

Solubility equilibria

Solubility Equilibria
Deals with substances whose solubility

are low Ksp (solubility product constant)

solubility of a precipitate in water Saturated : Ksp = IP Unsaturated : Ksp > IP Supersaturates : Ksp < IP

Equilibrium constant expressing the

Factors that influence solubilitites

Common ion effect

A precipitate is less soluble in a solution containing an excess of one of the ions common to the precipitate than it is in pure form An increase in solubility occurs when salts that contain no ions in common with the precipitate are present in the solution

Diverse ion effect

Ksp,actual = Ksp,apparent/

In such case, the actual Ksp is derived by dividing apparent solubility product constant by powers of mean ionic activity coefficient, , which is the measure of the effectiveness with which a chemical species influences equilibrium

Debye-Huckel Limiting Law Expression

-log = 0.512 Z+Z- = 0.5 CiZi2

where: - mean ionic activity coefficient Z charge of ions ionic strength

temperature

Generally, solubility increases with increasing temperature The lower the pH the higher the solubility Presence of complexing agents such as ammonia increases solubility

pH

complex formation

Solubility rules
All nitrates,

acetates and perchlorates are

soluble All halides (except F-) are soluble, except with Ag+, Hg2+ and Pb2+ All sulfates except Ba2+ and Pb2+ are soluble, but Ca2+, Ag+, Hg2+, and Sr2+ are only slightly soluble All sulfides are insoluble except with IA and IIA elements and (NH4)2S All other common inorganic compounds are insoluble except Ba(OH)2 and Sr(OH)2 which are soluble. Ca(OH)2 is only slightly soluble

Ag+ determination Cl- determination Titrant Indicator

VOLHARD Direct Indirect KSCN Fe3+

MOHR Indirect Direct AgNO3 CrO42-

FAJAN Direct Direct DCF-

Acidity/basicity Precipitation rxn Titration rxn Indicator rxn Color change

Acidic Ag+ + ClAg+ + SCNFe3+ + SCNBrick red

Neutral to basic Ag+ + ClAg+ + ClAg+ + CrO42Yellow orange

Acidic

Pink

Permanganimetry
Uses KMnO4 as oxidizing agent (titrant)

Permanganate processes where KMnO4 is

used as titrant are self-indicating titration i.e. endpoint is a permanent faint pink color Primary standards for KMnO4:
AsO3 Na2C2O4 Pure Fe metal

Other REDOX Titration

Dichromate Process ( using K2Cr2O7

as titrant)

Indicator: sodium/barium diphenylbenzidine sulfonate Color change: colorless to red violet the oxidizing agent I2 solution is the titrant Indicator: starch solution End point: deep blue solution Used for determining substance with oxidizing properties Titrant: Na2S2O3 (reducung agent) Indicator: starch solution End point: disappearance of blue color

iodometry (direct titration with iodine)

I2 is

iodometry (indirect titration with I2)

Electrochemistry

Electrochemistry
Electrochemical cells
Consists

mainly of 2 electrodes which are immersed either into the same solution or into 2 different solutions in electrolytic contact with one another

Galvanic/Voltaic Cell

Electrolytic Cell

1. Energy

Chemical reaction furnishes electrical energy

2. Electrode rxn 3. Anode rxn

Spontaneous Oxidation

4. Cathode rxn 5. Anode polarity 6. Cathode polarity

Reduction +

Chemical reaction is forced to proceed by application of electrical energy Non-spontaneous Oxidation Reduction + -

Schematic representation for electrochemical cells

Convention:
Constituents comprising the cell are listed in the

order in which they would be encountered if we begin at the anode and traveled through the cell solutions to the cathode Use conventional symbols for ions, elements, molecules / - boundary between 2 phases // - salt bridge , - indicates that the species are at the same phase