Analytical Chemistry

Julie Anne del Rosario

Outline
Analytical Chemistry

Concentrations
Chemical Equilibria Titration Electrochemistry Spectral measurements

Analytical Chemistry
Branch of chemistry that deals with the

separation, identification and composition of matter

Qualitative what is present

Quantitative how much is present

Analyte components of a sample that are to be

determined

Importance of Analytical Chemistry

Product development

Pollution control
Fundamentals of research

Methods of Analysis
1.
1. 2.

Classical Methods
Gravimetric
Example: precipitation

Volumetric
Example: titration

2.
1.

Modern/Instrumental Methods
Spectroscopic 2. Potentiometric

Precision vs Accuracy
Precision closeness of data to other data that

have been obtained in exactly the same way

Accuracy closeness of the experimental result

to its true or accepted value

Precipitation method
Sample is dissolved in appropriate solvent. 2. A precipitant is used to convert the analyte into a sparingly soluble precipitate 3. The precipitate is converted into a product of known composition by a suitable heat treatment 4. The percentage of the analyte in the sample is calculated using a gravimetric factor (GF) . % = 100% . =
1.

 Suppose we wish to calculate the mass of S in g

from BaSO4 ppt of known mass.

2 2+ + 4 4()

Volumetric method
Standard solution solution of known concentration Standardization process of determining the concentration of an unknown solution Primary standard a substance of high purity used for standardization
Rapid reaction Simple balanced equation Complete no side reactions Appropriate indicator is available

Titration
Slow addition of one solution of a known concentration (called a titrant) to a known volume of another solution of unknown concentration until the reaction reaches neutralization, which is often indicated by a color change.

Direct Titration the analyte reacts with the standard

solution directly Back Titration an excess standard solution is added and the excess is determined by the addition of another solution Replacement titration the analyte is converted to a product chemically related to it and the product of such reaction is titrated with a standard solution

Ways of Expressing Concentration

1. Molarity, M =

*What is the molarity of pure water? 2. Molality, m =

3. Mole fraction, x

= +

Ways of Expressing Concentration

4. Normality, N =

5. Formality, F (for ionic compounds) = 6. Weight % % = 1005

Ways of Expressing Concentration

7. ppm by weight

8. ppb by weight

Exercises
1. A solution is prepared by dissolving 0.1164g of (NH4)2Ce(NO3)6 (FW=548.3) in 2.56L H2O. Calculate the ppm of NH4+. 2. Calculate the molar analytical concentration of solute in aqueous concentration that is 11.00% (w/w) NH3 and has a specific gravity of 0.953. 3. A 0.3396 g sample assayed 96.44% Na2SO4 was titrated with a solution of BaCl2:
2 2+ + 4 4() What is the molarity of the BaCl2 solution if the endpoint was observed when 35.70mL of the reagent was added?

Exercises
4. A solution is prepared by dissolving 9.88g of trichloroacetic acid Cl3COOH (FW 163.39g/mol) in water and diluting to a volume of 500mL. At this concentration, the acid is about 70% dissociated. Calculate a.) the formality of the trichloroacetic acid, b.) molarities of the species Cl3COOH and Cl3COO-. 5. Give the equivalence weight of each reactant in the following unbalanced reactions: . + 2 2 + 2 . 4 + + 2 2() + + . + + . 2+ + 2 2

6. Suppose we wish to calculate the mass of S in g from BaSO4 ppt of known mass.
2 2+ + 4 4()

7. What is the normality of a sulfuric acid solution that is 18 M?

Exercises
8. The sodium and potassium in a sample weighing 0.9250g are converted into NaCl and KCl salts. The chloride mixture weighs 0.6065 g. The chlorides are then converted into Na2SO4 and K2SO4. The mixture weighing 0.7190g. Calculate the percentages of Na2O and K2O in the original sample.

Chemical Equilibrium
Ratio of concentrations of reactants and products

is constant Ratio of forward and backward reactions are the same.

RECALL: What law states that the position of chemical equilibrium always shift in a direction that tends to relieve the effect of an applied stress?

Le Chateliers Principle
Applied stress
Changes in temperature Pressure (gas) Total concentration (mass action effect)

A+BC+D

Equilibrium Calculations
Mass balance equations 2. Equilibrium constant expressions 3. Charge balance equations
1.

Electrolytes
Strong Weak

1. Inorganic acids: HNO3, HClO4, H2SO4, HCl, HI, HBr, HClO3, HBrO3. 2. Alkali and alkalineearth hydroxides 3. Most salts

1. Many inorganic acids, including H2CO3, H3BO3, H3PO4, H2S, H2SO3 2. Most organic acids 3. Ammonia & most organic bases 4. Halides, cyanides and thiocyanates of Hg, Zn, Cd

Acids and Bases

BRONSTE ARRHENIU LEWIS D-LOWRY S Produces e- pair Proton ACID H3O+ in acceptor donor solution Produces BASE e- pair Proton HO- in S donor acceptor solution

Bronsted Lowry Acids

Acids and Bases

Conjugate Base species found when an acid

loses a proton Conjugate Acid species formed when a base accepts a proton
A compound that can act as either an acid or

a base, such as the H2O in the above examples, is called amphiprotic.

Calculation of pH
pH= -log (activity of H+) pOH= -log (activity of OH-) Ion-product of water (constant!): pH + pOH = 14

Exercises
Calculte the pH of the following: Strong acids
1. 0.06 M HCl 2. 0.02 M H2SO4

3. 1 x 10-10 M HCl
Strong bases
1. 0.5 M NaOH 2. Diluted 10-fold

Exercises
Weak Acids and Bases

pH = pK log [HA] pH = 14 pKb + log [B]

1. 0.01 M acetic acid, Ka = 1.8 10-5 2. 5 M aqueous ammonia, Kb = 1.8 10-5

Exercises
1.

The pH of a Ba(OH)2 solution is 10.0. What is the H+ ion concentration? What is the pH of the resulting solution made by mixing 25mL pf 0.1 M HCl and 15 mL of 0.1 NaOH? When 0.02 mole of a monoprotic acid is dissolved in 350 mL of water, the pH is 3.05. What is the ionization constant of the acid?

2.

3.

Hydrolysis of Salts
Reaction of dissolved salts with water, e.g.: A) Anion from a strong acid, cation from a weak base, e.g. NH4Cl: NH4+ + H2O NH3 + H3O+ Cl- + H2O no reaction pH is acidic B) Anion from a weak acid, cation from a strong base, e.g. NaHCO3: Na+ + H2O no reaction pH is basic HCO3- + H2O H2CO3 + OH-

Hydrolysis of Salts
Acidic Salt

pH = 7 log ([salt]/Kb)
Basic Salt pH = 7 + log ([salt]/Ka) *when [salt]/Kh >>> 1000

Buffer Solutions
Capable of maintaining pH of some fairly constant

value even when small amounts of acid or base are added Contains a conjugate acid-base
Weak acid + conjugate base (salt of weak acid)

Weak base + conjugate acid (salt of weak base)

Ex. HOAc NaOAC, NH3 NH4Cl

Henderson-Hasselbach eqautions
pH = pKa + log ([salt]/[acid]) pH = pKb + log ([salt]/[base]) Buffer effectiveness greatest when [salt]/[acid]=1 or [salt]/[base] = 1
0.01M HOAc + 0.01M NaOAc 0.001 M HOAc + 0.001 M NaOAc

Buffer capacity
Measure of buffer effectiveness in resisting

changes in buffer pH upon addition of strong acid/base

Number of moles of strong base required to

change the pH of 1L of buffer solution by 1 pH unit.

Exercises
1.

What mass in grams of NaC2H3O2 must be dissolved with 500 mL of 0.100M acetic acid to make a 2L of buffer solution of pH=5? Ka = 1.8 x 10-5

2.

What is the pH of 0.256 M NH4Cl? Kb,NH3 = 1.8x10-5?

What is the pH of the resulting solution made by mixing 5mL of 0.2178M HCl and 15mL of 0.1156M NH3?

3.

Titration Curves
Plots of a concentration related variable as a

function of reagent volume

Acid Base Titration

http://chemwiki.ucdavis.edu/Analytical_Chemistry/Quantitative_Analysis/Titration/AcidBase_Titrations

Acid-Base Titration

Applications of Acid-Base Titrations

1. Kjeldahl Titration
Determination of organic nitrogen

% N x factor = % protein 6.25 = meat 6.38 = dairy 5.70 = cereals 2. Mixture of Na2CO3, NaHCO3 and NaOH

Exercises
A 5.8734 g sample of beef was analyzed for its N

content and liberated NH3 was collected in a 50.mL of 0.4691 M HCl and 12.55 mL back titration with 0.0256 M NaOH was required. Calculate the percentage protein in the beef sample.

Double Indicator Method

Precipitation Titration
Mohr method (for halides and cyanides) 2. Volhard Method (for silver and for halides) 3. Fajans method
1.

Exercises
1.

In standardizing a solution of NaOH against 1.431 grams of KHP (MW = 304.22), the analyst uses 35.50mL of the alkali and has to run back with 8.25 mL of acid (1mL = 10.75 mg NaOH). What is the molarity of the NaOH solution?

2.

A solution that may contain NaOH, Na2CO3 and NaHCO3, alone or in compatible combination was titrated with .1200 M HCl. The volume of the acid required to reach the phenolphthalein endpoint was 25.67 mL while 38.13 mL to reach the methyl red endpoint. What are the components of the mixture?

Exercise
3. A sample consisting of Na2CO3, NaOH and inert matter weighs 1.179 g. It is titrated with 0.2239 M HCl with a phenolphthalein as the indicator, and the solution became colorless after the addition of 45.62 mL. Methyl orange is then added and the 12.85 mL more of the acid are needed for the color change. What is the percentage of Na2CO3?

Electrochemistry
Oxidation reaction involves an increase in the

oxidation state of an element Reduction reaction involves decrease in oxidation state

Ce4+ +Fe2+ Ce3+ + Fe3+ Loss of Electrons Oxidation Reducing Agent Gain of Electrons, Reduction, Oxidizing Agent

Electrochemical cells
Cathode reduction

Anode oxidation

Galvanic or voltaic cell chemical to electrical energy Electrolytic cell electrical to chemical energy

Electrochemical cells

Absorption of Radiation: UV-Vis

Exercise
1. A solution containing 4.49ppm KMnO4 has a transmittance of 0.576 in a 1.00 cm cell at 520 nm. If the transmittance of an unknown solution is 0.735, what is the concentration of the unknown KMnO4 solution in ppm?

Exercises
1. Complete and balance the redox reaction where ClO3- reacts with HNO2 in an acidic solution to produce Cl2(g) and NO3-. 2. Balance the two half-reactions

Cr2O72- + 14 H+ + 6 e- --> 2 Cr3+ + 7 H2O H2C2O4 --> 2 CO2 + 2 H+ + 2 e3. What is the percentage of MnO2 in a 500 mg sample which after the addition of 80.00 mL of 0.1056 M Fe2SO4 solution required 8.50 mL of 0.0867 M K2Cr2O7?