INTRODUCTION TO ANALYTICAL CHEMISTRY

Analytical chemistry

identification of sample constituents (qualitative analysis) determination of relative amounts of sample constituent(s) (quantitative analysis)

ANALYTE

sought for or desired constituent in a sample

Type of analysis according to extent

1.

2.

3.

complete or exact ultimate proximate or partial

Complete or exact analysis

the amount of each constituent of the sample is determined quantitatively Example: blood chemistry involves the determination of glucose, sodium, potassium, triglycerides

Ultimate analysis

the amount of each element is determined Example: analysis of gasoline reports %C, %H, %O, %Pb, etc % elements

Proximate or partial analysis

the amount of a selected constituent in a sample is determined Example: partial analysis of aspirin tablets gives the amount of salicylic acid impurity crude fat or crude fiber in animal feeds

Type of analysis according to level of analyte

1.

2.

3.

4.

based on classification of analyte major constituent > 1% of the sample minor constituent 0.01 1% of the sample trace constituent 0.001 0.01% of sample ultratrace constituent < 0.001% of sample

Type of analysis according to amount of sample

MASS OF SAMPLE
VOLUME OF SAMPLE

ANALYSIS

macro semimicro micro ultramicro

> 100 mg 10 100 mg 1 10 mg < 1 mg

> 100uL 50 100 uL < 50 uL ---

Example

What type of analysis was performed on a 0.500 g sample of animal feeds which was found to contain 1.35% zinc?

A.

B.

C.

D.

a complete macroanalysis of a major constituent a partial macroanalysis of a minor constituent a partial macroanalysis of a major constituent a complete macroanalysis of a minor constituent

MOISTURE DETERMINATION

analytical results are reported based on a. as-received sample b. oven-dried sample

A 1.000 g as received soil sample has a moisture content of 14.00%. The oven-dried sample, which is completely moisture-free, has an 18.00% Na. Find the % Na in the sample on an as-received basis.

Solution 1:
as-received
14.00 x 86

oven-dried
0 18.00 100

% water % Na % non-volatile material

x/86 = 18/100 x = 15.48% %Na as recvd/% NVM = % Na oven-dried/%NVM oven dried

Solution 2:

g H2O = (1.000)(14.00/100) = 0.1400 g gNVM = g asrcvd g H2O = 1.000 0.1400 g = 0.8600 gK = gNVM x %Na = 0.8600(18.00/100) = 0.1548 gK

%Na asrcvd = gNa/gasrcvd x 100

= 0.1548gNa/1.000g x 100% = 15.48% Na

Review of Stoichiometric Concepts

Molarity, M

moles solute/liter solution mmoles solute/mL solution refers to species concentration

Analytical molarity, Cx

Formality total number of moles of solute regardless of its chemical state per liter of solution or mmoles /mL refers to analytical or total concentration describes how a solution of a given molarity can be prepared

Example:

A 1.0 M NaOH solution is more accurately described as 1.0 F NaOH. Why? There are no NaOH molecules in solution

Example:

Given a 0.100 F CH3COOH solution: CHOAc = [HOAc] + [OAc-]

0.100 F HOAc = 0.0987 M + 0.0013 M

since 0.100 M HOAc is 1.3% dissociated

Normality, N

= the number of equivalents of solute per liter of solution = meq solute/mL solution _g solute_ EW solute

the number of equivalents =

Calculating Equivalent Mass/Weight

EM = FM/n where FM = formula mass n = value dependent on rxn = in eq/mol or meq/mmol

Determining the value of n:

1.

2.

3.

Acid-base reaction Oxidation-reduction reaction Precipitate formation and complex formation

Acid-base reaction

Acid: n is the number of replaceable or acidic H+ according to the reaction Base: n is the number of H+ required to neutralize each mole of a base

Example:

H3PO4 + 2NaOH NaH2PO4 + 2H2O

EM H3PO4 = FM/2 N = g/(FM/2)/L Why? Phosphoric acid has two acidic H+ per mole phosphoric acid EM NaOH = FM/1 Why? 2 moles NaOH reacted with 2 moles H+ or 1 mol H+ required to neutralize 1 mol NaOH

Oxidation-reduction reaction

n is the number of electrons gained or lost in the reaction per mole of the species

NOTE: to get n, the equation need not be completely balanced BUT the ATOMS which gained or lost electrons have to be balanced

Example

MnO4- + C2O42- Mn2+ + CO2

EMKMnO4 = FM/5 Why? MnO4- to Mn2+ involves 5eEMK2C2O4 = FM/2 C2O42- CO2 Why? each C atom lost 1 e-, thus 2 carbon atoms lost 2 electrons

Precipitate and complex formation

metal cation: n = charge of cation anion: n = the number of metal ion equivalents that one mole of the anion reacts with

Examples:

1. Ag+ + Cl- AgCl EMAgNO3 = FM/1 EMKCl = FM/1

2. Ba2+ + SO42- BaSO4 EMBa(NO3)2 = FM/2 EMNa2SO4 = FM/2

3. Ag+ + 2CN- Ag(CN)2EMAgNO3 = FM/1

EMKCN = FM/1/2 = 2FM Why? 1 mol CN- reacts with metal ion equivalents since 2 mol CN- reacts with 1 metal ion equivalents

Cu(NO3)2 + Na3PO4 Cu3(PO4) 2 + NaNO3 EM Cu(NO3)2 = FM/2 EM Na3PO4 = FM/3 EM Cu3(PO4) 2 = FM/6 EM NaNO3 = FM/1

3Cu(NO3)2 + 2Na3PO4 Cu3(PO4) 2 + 6NaNO3

Cu2+ + 4CN- Cu(CN)42-

EM Cu(NO3)2 = FM/2

EM KCN = 2FM Why? 4 mol CN- reacts with 2 metal ion equivalents 1 mol CN- reacts with 2/4 metal ion equivalents OR metal ion equivalents

Relation between N and M:

N = nM

N = __g__ x __1__ = _g_ x _n_ = n moles = nM V MW V V MW n

Significance of Normality:

aA + bB products

at the endpoint: equivalents A = equivalents B (the hope is the equivalence point is achieved, and the stoichiometric point is reached) THUS, NAVA = NBVB OR meqA = meqB

Titer Methods

Titer weight of pure substance corresponding to 1 mL of solution

Corresponding means: will react exactly with is chemically equivalent to is contained in may be obtained from may be substituted for

Titer

states the weight of some substance other than the solute with which 1 mL of solution will react exactly

Titer units: weight = _mg_ volume mL

= mg reactant/substance mL solution

Example:

If 1.00 mL HCl(aq) neutralizes 4.00 mg NaOH, HCl + NaOH NaCl + H2O

n=1 1 meq acid = 1 meq base Titer = 4.00 mg NaOH = 4.00 mg mL HCl mL

From normality units:

N = ___mg____ = meq mL x EW mL

Titer = Nsoln x EWreactant Note: EW of substance with which the solution reacts

Example:

It the titer = 4.00 mg/mL N = __T__ = _4.00 mg/mL_ EW 40.00 mg/meq N = 0.1000 meq/mL

Example:

What is the NH3 titer of a 0.120 N solution of HCl? T = 0.120 meq x 17.0 mg NH3 = 2.04 mq NH3 mL meq mL HCl

Note: NH3 + HCl NH4Cl 1 meq NH3 = 1 meq HCl

Example:

Calculate the normality of an HCl solution having a Na2CO3 titer of 5.00 mg/mL.

Na2CO3 + HCl 2NaCl + H2CO3 EW Na2CO3 = FW 2 or 106 mg Na2CO3 = 2 meq HCl T = Nsoln x EWreactant

N = 5.00 mg Na2CO3 x mL HCl

__1 meq HCl__ 53.0 mg Na2CO3

N = 0.0943 meq HCl mL HCl

Determining the g solute:

g solute = EW solute x N reactant x liter solution

g solute = EW solute x Titer (mg/mL) x mL soln EW reactant x 1000 (mg/g)

Example:

How many g of AgNO3 (169.9) would be used to prepare 500.0 mL of a solution that has a chloride (35.45) titer of 0.5000? g AgNO3 = 169.9 mg x 0.5000 mg Cl- x 500 mL meq mL Ag+ ___________________________ 35.45 mg x 1000 mg meq q g AgNO3 = 1.198

Example:

Calculate the Na2CO3 (EW 53.00) titer of a 0.1037 N HCl solution. x 53 mg Na2CO3 1 meq HCl

Titer = 0.1037 meq HCl mL HCl

Titer = 5.496 g Na2CO3 mL HCl