CHEM 26 Analytical Chemistry

Introduction

Analytical Chemistry

- Measurement science consisting of a set of powerful ideas

that are useful in all fields of science and medicine

- The branch of chemistry that deals with separation,

identification, and determination of the components in the

sample.

Quantitative Analysis Qualitative Analysis

- Discusses indicated - Reveals the identity of

amounts elements and compounds

- Numerical and specific - Is biased and subjective

Role:

- Applied throughout industry, medicine, and all sciences

- Plays a vital role in researches

Types of Chemical Analysis

- Volumetric Methods

- Gravimetric Methods

- Electroanalytical Methods

- Spectroscope Methods
Steps in Chemical Analysis

1. Formulate a question

2. Select analytical procedure

3. Sample preparation

4. Analysis

5. Reporting and interpretation

6. Drawing conclusion

Units, Concentration, and Stoichiometry

Measurements

- The assignment of a number/attribute to a characteristic of

an object or events which can be compared with other

objects/events

- Dependent on the context and the discipline of study

- Consists of a type, magnitude, unit, and uncertainty

Quantity
 - one that can be measured and consists of a magnitude and

unit

Types of quantities

- Base

o Basic building quantities

- Derived

o Derivations from base quantities

Magnitude

- Numerical value and given number

- Given by the measuring instrument

- Provides benchmark data

Units

- Provides directionality to the magnitude

- English

o Old system of units

o Variable definition

o Almost obsolete

- Metric

o Widely used
 o Standard units

o French Systeme Internationale d’Unites (1960)

- Involves standardization

o Cesium clock oscillation – 1 second

o Platinum Iridium cylinder – standard kilogram

The mole

- Mol

- SI unit for amount of a chemical species

- Associated with the chemical formula

- Represents Avogadro’s number

o 1 mol of substance = 6.022 x 1023 no. of atoms

Millimoles

- 1/1000 of a mole

- Millimolar mass, mM = 1/1000 of a molar mass

n – number of moles

Mass – Gx

Molar Mass - Mx
Uncertainty

- Precision: how closely individual measurements agree to one

another

- Accuracy: how individual measurement agree with the

correct/true value

Significant figures

- Exact and inexact numbers

- Measured values are inexact

- The last digit reported always has uncertainty

- Constant significant figures are not followed (i.e.

conversion factors and molar mass)

Unit Analysis

- Dimensional analysis

o Units are multiplied, divided, and cancelled out to

arrive at the desired unit of results with use of

conversion factor

o Conversion factor: expressed as a ratio of same

quantities of different units

Common Measurements and Sources of Common Error

⌂ Mass: refers to the amount of matter in an object;

independent of the object’s location

⌂ Weight: the pull of gravity on an object; dependent on

location

⌂ Volume: refers to the amount of space occupied by an object

o Liquids: Graduated Cylinder

o Regular shaped solids: V=lwh

o Irregular shaped solids: Water displacement

⌂ Density: ratio of mass per unit volume

⌂ Specific gravity: ratio of the density of a liquid/solid

over the density of water at 4 degree Celsius; SG is

unitless

⌂ Temperature: measure of hotness/coldness of matter;

indicates the energy of particles

Absolute Zero Temperature = 0 Kelvin

 - All vibrations stop

- 0 Kelvin has not been reached ever

Types of Error:

- Systematic/Determinate Error

o Can be attributed to a definite cause; operative,

method, and instrumental

o Affects the accuracy, reproducibility

- Random/Indeterminate Error

o Inherent to the measuring device

o Cannot be reduced; affects the precision

- Gross

o Severe enough that the analysis needs to be repeated

o i.e. outliers, spills, and overtitrations

Solution and their Concentration

⌂ Molar Concentration

o No. of moles of a species that is contained in the

liter of the solution

o Unit: Molar; M

Analytical Molarity
 - Total no. of moles of a solute in 1L solution

- Specifies a recipe by which the solution can be prepared

Equilibrium Molarity

- Expresses the molar concentration of a particular species

in a solution at equilibrium

- 1M H20: 1M NaCl

⌂ Normality

o No, of equivalents of a species that is contained in

1L of solution

- For acids: no. of H dissociated

- For bases: no. of OH dissociated

- Salt: no. of positive ions

 - Redox: change in oxidation

Percent Concentrations

⌂ Mass percent (w/w) = (mass solute/mass solution) x 100%

⌂ Volume percent (v/v) = (volume solute/volume solution) x

100%

⌂ Mass/Volume percent (w/v) = (mass solute/volume solution) x

100%

PPM, PPB, PPT

ppm

- parts per million

- mg/L

ppb

- parts per billion

- 1 µg/L

ppt

- parts per thousand

- g/L

Unit Conversion Table

Unit Symbol Notation

Kilo k 3
Deci d -1

Centi c -2

Milli m -3

Micro µ -6

Nano n -9

P-function

- Negative logarithm to base of 10 of the molar concentration

of species

Chemical Stoichiometry

- defined as the quantitative relationship among reacting

species

- Includes balancing equations

Principle of Dilution

⌂ [] – Concentration in molarity

⌂ Usually given in moles per liter

⌂ Solute – the one being dissolved

⌂ Solvent – the one that does the dissolving

⌂ A solution is prepared by dissolving a solute in a solvent

⌂ When a solution is diluted, the number of moles stay the

same, but the concentration changes

 ⌂

Methods of Analysis

Classical Method

- Wet method

- Extraction, distillation, gravimetry, and titrimetry

Instrumental Method

- Spectrophotometry

- Conductivity

- Potentials

Titrimetry

- Analysis based on the determination of the quantity of a

known concentration reagent to react with the analyte

Volumetric Titrimetry

- Volume of a standard reagent is the measured quantity

Terms:

- Standard solution: reagent of a known concentration

- Analyte: species to be tested

- Titration: adding of standard solution to the analyte until

the reaction is judged to be complete

Sample:
 Find the Molarity of CH3CH2OH when 2.30 grams of CH3CH2OH

were mixed with H2O to make 3.50 L of solution

Molarity of Potassium ion that contains 63.3 ppm of

K3Fe(CN)6

- Back Titration: additional of excess amount of titrant and

titrate excess with another standard solution

- Equivalence point: Quantity of added titrant is the exact

amount necessary for stoichiometric reaction with the

analyte

- End point: what is actually measured; marked by the sudden

change in the physical property of the solution; occurs

from the addition of a slight excess of titrant

- Titration error: difference between the endpoint and

equivalence point; can be calculated via blank titration

- Indicators: added to the analyte solution to produce

observable results

- Primary Standard: highly purified compound that serves as

reference material

o High Purity

o Atmospheric Stability
 o Absence of hydrate

o Reasonable Solubility

o Large Molar Mass

o Modest Cost

- Blank Titration: Titration without the analyte; determines

the amount of titrant needed for an endpoint to occur

- Direct method: direct weighing of a primary standard and

dissolving in a solvent

- Standardization: titrant to be standardized is used to

titrate a quantity of primary standard; the result becomes

a secondary standard

Equations for determining concentrations

REDOX

- Oxidation: loss of electron

- Reduction: gain of electron

 - Oxidizing agent: one being reduced

- Reducing agent: one being oxidized

Rules:

⌂ Oxidation no. of elements on their free state is zero

⌂ Oxidation no. of monoatomic ion is same as its charge

⌂ In binary compounds, halogens have a -1 oxidation no. when

bound to a less electronegative element

⌂ When in compound, hydrogen has an oxidation number of +1.

When combined with a less electronegative element, the

oxide tion no. becomes -1

⌂ The oxidation no. of oxygen is usually -2 in compounds of

peroxides. It is -1, w/fluorine it is +1.

⌂ For all neutral compounds, sum of oxidation no. of all

elements must be equal to zero

⌂ In polyatomic ions, the sum of oxidation no. of all atoms

is equal to the net charge of the ion.

Steps

1. Balance the equation

2. Tackle each half reaction

3. Balance the hydrates

4. Balance the charges

5. Multiply/Cancel out the added electrons

Back Titration

- Additional of excess titrant

- To make sure of positive/observable result occurs

- An additional standard solution is required

Gravimetric Method of Analysis

- Quantitative method based on measuring the mass of pure

compound, chemically related to the analyte

- Most accurate; mass is measured with great accuracy

- Disadvantage: lengthy and tedious process

Types:

- Precipitation Gravimetry

o Common method used

o Analyte is separated from the solution as a

precipitate of a compound of known concentration and

weighed

- Volatilization

o analyte is converted from the sample via gas

conversion
 - Electrogravimetry

o Analyte is separated by deposition of an electrode

using electric current

Precipitation Gravimetry

- Analyte is converted to precipitate – filtered and wash

free of impurities; converted to a product of known

concentration then weighed

Steps: Precipitation Gravimetry

1. Preparation of the solution (mother liquor)

o Adjustments are made for optimum precipitation

2. Precipitation

o Addition of precipitating agent

o Upon addition of the first drop, super saturation

occurs and nucleation starts

o Continuous addition refers to continuous

nucleation/particle growth

o Precipitate Formation Mechanism

 ▪ Nucleation: formation of a stable solid due to

atoms, ions, or molecules joining with one

another

▪ Particle growth: aggregation of existing nuclei,

forming larger and settling particles

o Colloidal Suspension Formation; formation of small

particles

o Von Weimarn Equation

▪ Particle size is inversely proportional to

relative supersaturation

o Q: Concentration of reactant prior to precipitation

o S: Solubility of Precipitate

o To avoid further nucleation: increase the solubility,

decrease the concentration of reactant

o Optimum conditions

▪ Precipitation using dilute solutions, results to

low Q

▪ Slow addition of the precipitating agent, results

to low Q

▪ Stirring to avoid concentration sites, results to

low Q

▪ Hot filtration/precipitation, results to high S

▪ pH adjustment (high S), but not too much

 ▪ Precipitation from homogenous solution

3. Digestion

o Precipitate is left hot (below boiling point) for

particles to digest

o Around 30 mins to 1 hour

o Involves dissolution of small particles and

reprecipitated on larger ones

o Good for colloidal precipitate – forcing small

colloidal particles to agglomerate

4. Washing and Filtration

o Remove surface adsorbed species (particles attached to

the surface)

o Solvent must be carefully chosen to avoid peptization

o Peptization

▪ Process of forming dispersed colloidal suspension

▪ Can be hasten by too much wasting

▪ Washing agent used i.e. dilute nitric acid,

ammonium nitrate, acetic acid

o Common Ion Effect

▪ Upon too much excess of agent

o Induces solubility of precipitate

 o Precipitating agent must be added in 50% Excess Only

Sample: To precipitate 10 moles of Ag+ as Ag2S, how many

moles of agent is needed

o Set up equation

o Balance the equation

o Determine the needed moles of the agent by basing on

the needed moles of the analyte

To have 10 moles of Ag+, multiply the product by 5,

which the resulting S2- will have 5 moles

o Multiply the acquired moles of the agent by 50% to

find the excess, then add to the original

5. Drying/Igniting

o Drying: Oven at 100 to 150o; removal of excess moisture

o Ignition: Muffler furnace 600-1200o C; to get the

material with composition

o Ex. CaC2O4 is hydrophilic, so it is ignited to CaCO3 or

CaO

6. Final Weighing/Calculation
 o Use of ashless filter paper to be headed in a crucible

and constantly weighed

Impurities

o Coprecipitation: occlusion of an impurity after the

analyte

o Post precipitation: precipitation of an impurity after

the analyte; can be reduced by ready filtering the

precipitate; another precipitate is present

Precipitating agent

Calculations

Gravimetric factor: ratio of analyte to the precipitate

R: ratio of moles of analyte and principle