Analytical Chemistry - a branch of chemistry involved with the analysis of chemical substances. 2 Main Divisions 1.

Qualitative Analysis Concerned with the identifying substances by understanding how different substances react with solvents and with each other. It is possible to deduce their identity by performing systematic tests on them and the rest might include. a. Solubility Test to see if a solid dissolves in a solvent b. Precipitation Test to see if a solid formed when two dissolves substances are mixed. c. pH Test to determine the concentration of dissociated [H] atoms. d. Flame Test to see what color is produced when the substance is burned 2. Quantitative Analysis Deals with the determination of amounts or concentrations of the constituents Classification of Quantitative Analysis 1. Complete or Ultimate Analysis the amounts of all the constituents in the sample were determined. 2. Partial Analysis only same are determined 3. Elemental or molecular analysis refer to the determination of the amounts of elements and molecules 4. Major Constituents of Macro Analysis implies that the constituents determined was present in high concentrations 5. Trace Analysis constituents determined was present in low concentrations Division of Quantitative Analysis A. Gravimetric Methods the constituent to be determined, w/c is the analyte, is isolated, either as an element or as a compound of definite composition. This B. element or compound is weighed, and from its weight and its known chemical composition, the amount of the design constituents is determined. 1. Chemical Precipitation Methods 2. Electronic Deposition Methods C. Volumetric Methods a well defined reaction is cause to take place, where in the reagent is added from an apparatus so designed that the volume of the solution employed to complete the reaction can completely be measured.

1. Chemical Indicator Methods 2. Electrometric Methods a. Potentiometric b. Conductometric c. Amperometric d. Coloumetric D. Colometric Methods the substance to be determined is converted to some compound which imparts to its solution a distinct color, the intensity of w/c varies in proportion to the amount of the compound in the solution. Such a solution is compared to a standard. E. Other Physiochemical Methods measure properties such as turbidity of suspension of semi-colloidal precipitates, the degree to w/c the plane is polarized light is rotated by certain solution, the intensity of spectrum lines, and the degree of refraction. F. Gas Volumetric Methods quantitative determination of the components of mixture gases. Steps in an analysis 1. Overall Plan or Goal 2. Collecting the sample 3. Measuring the sample 4. dissolving the sample Solvents a. water b. acids c. organic solvents d. fusion 5. Dealing with potential inferences 6. Treating the sample and measuring the analyte 7. Calculating the amount and evaluating the result Review of some basic principles 1. Precipitates downward pointing arrow or underline 2. Gases with symbol (g) or upward pointing arrow CaCo3 + 2H+ Ca+2 + H2O + CO2 3. Only this constituents actively taking part in a chemical reaction are included in the reaction Ba+2 + SO4-2 BaSO4 BaCl2 + NaSO4 BaSO4 + 2NaCl

4. In cases where the reactant or product exists in equilibrium with its constituents parts, only that form present in the greatest amount is included in the rxn: a. Ferric Nitrate Solution + Sodium Hydroxide Solution Fe+3 + 30H- Fe(OH)3 b. Ferric Nitrate Solution + Ammonium Hydroxide Solution Fe+3 + 3NH4OH Fe(OH)3 + 3NH+4 Fe+3 + 3NH3 + 3H2O Fe(OH)3 + 3NH+4 c. Zinc Sulfide Suspension + Hydrochloric Acid ZnS(s) + 2H+ H2S(g) +Zn+ d. Cuppric Ammino Sulfate Solution + Acetic Acid Cu(NH3)4+2 + 4HC2H3O2 Cu+2 + 4NH+ + 4CH3COO e. Ferrous Sulfate + Potassium Dichromate (acidic solution) 6Fe+2 + Cr2O7-2 + H+ 6Fe+3 + 2Cr+3 + 7H2O II. Acids, Bases and Salts Hydronium Ion - H3O+ or H2O.H+ - solvated proton Acid - substance w/c in solution gives a hydrogen ion concentration - solute that increases the anion solvent of the computer Base - substance w/c gives a hydroxyl ion - solute that increases the anion concentration of the solvent Salt substance formed when electron are transferred from one atom to another to form an ionized particles held together by electrovalents bonds. Bronsted Lawry Theory Acid substance that can donate protons Base substance that can take proton from an acid Acid .H+ + Base Conjugate acid-base pair

Methods of Expressing Concentration

Concentration =

wt of solute

unit volume of so ln

A. Grams per unit volume g solute Concentration = L So ln B. Percentage Composition g solute Concentration = g So ln C. Specific Gravity subs tan ce Specific gravity = H2O at ref. D. Volume Ratios E. Molar and Formal Solution Molar Solution containing grammolecular weight of solute in a liter solution or moles of solute per volume (liter) solution F. Normal Solution g solute Normality = molecular weight. N = fM Sample Problem ( Preparation of Solution) 1. What is the normality of a solution prepared by dissolving 25.20g oxalic acid in sufficient water to give 1.2 liters of solution? What is the Molarity of the solution?
25.20 g 1 Normality = 126.1 1.2 = 0.3330N 2

M = N/f =0.1665

2. What volume of 0.15N reagent is needed for the preparation of 500ml 0.1N solution? 0.1
meq 500ml = 50 meq ml

50 meq Volume required = 0.15 meq = 333.3 ml ml

By formula of dilution: N1V1 = N2V2 (0.15)V1 = (0.1)(50) V1 = 333.3ml 3. A sample of impure oxalic acid w/c weighs 0.4750g requires 35.50ml, 0.2 N NaOH. Calculate the percentage oxalic acid in the sample? Milliequivalent base = milliequivalent acid 0.2
meq 35.60 ml = 7.120 meq ml

Milligrams oxalic acid =

126.1 mg 2 meq

mmol 7.120meq = 448.9 mg

mmol

% Oxalic Acid =

0.4489 100% = 94.51% 0.4750

4. A sample of impure calcite, w/c weighs 0.4950 is dissolve in 50ml of standard acid, and excess acid is titrated with 5.25 ml standard base; 1.0ml of acid is equivalent to 0.0053g sodium carbonate; 1.05ml acid = 1.0ml base, calculate the percentage of calcium carbonate in the sample.

Mass of sample = 0.4950 g 1.0 ml acid = 0.0053g Na2CO3 1.05 ml acid = 1.0 ml base Equivalent weight of Na2C03 ( complete neutralization) Weight of mol in grams 106 eq/mol 2 eq wt. in grams 53.0

5.30 mg
Normality =

53 mg

ml

= 0. 1

meq

meq ml

Net Volume Acid required for titration of sample = 50ml ( 1.0 ml base 5.25 ml base ) = 44.49 ml
1.05ml acid

meq acid = meq CaCo3 meq CaCo3 = 0. 1

meq (44.49ml) = 4.449 meq ml

mass CaCo3 =

100.1 mg 2 meq

mmol x 4.449 meq = 222.7 CaCo 3

mmol

% CaCo3 = 495.00mg x 100% = 44.99%

222.7 mg

Equilibrium Constants A + B C + D
d [ A] d [ B ] = = k ' [ A][ B ] dt dt d [C ] d [ D] = = k ' [C ][ D ] dt dt

[C][D] k ' = =k [ A][B] k"

A + 2B C + D

[C ][ D ] =k [ A][ B ] 2

Generally: aA + bB cC + dD
[C ]C [ D ] D =k [ A] A [ B ] B

} Law of mass action

Low Product Constant Water H2O H+ + 0HMass Action Constant

[H + ][0H - ] = k constant unity = 1 [ H 2 O] 2
@ 25 o C 1.0 x 10 14 1.2 x 10 15
13 5.8 x 10

Kw = [H +][0H - ]

0o C 100 o C

pH and pOH first process by sorensen pH = -log [H+] Ionization Constant Consider: NH3 + H20 (NH4OH) NH4+ 0H@ equilibrium
K NH 4OH

pH + pOH = 14

the ionization of a weak acid or a weak base furnishes an excellent example of reversible reaction

[ NH 4 ][OH ] = 1.75 x 10 5 = [ NH 4 OH ]

@ 25 o C

Much better as

K NH 3

[ NH 4 ][OH ] = [ NH 3 ]

Another CH3COOH CH3COO- + H+

[CH 3 COO ][ H + ] [CH 3 COOH ]

K NH 3COOH =

Common Ion Effect on Weak Acids and Bases Buffered Solution solution of weak acids or weak bases, in w/c the dissociation is cutdown by the presence of common ion change resistant to pH

Example : A solution of formic acid (HCOOH) is prepared by dissolving 1.15g of pure acid in water and diluting to 250ml. What is the concentration of the acid in mol/l? If tge acid in this solution is 4.6% ionized, what is the molar concentration of H+, HCOO- , and undissociated HCOOH in the solution. MW = HCOOH = 46 1.15g HCOOH ( M= (
1 mol HCOOH ) = 0.025 mol HCOOH 46 g

Getting the concentration

0.025 mol HCOOH ) = 0.1 M 0.250 L

HCOOH HCOO- + H+ 0.1 - x x x Since 4.6% has been ionized, then [H+] = 0.1 M (4.6/100) = 0.0046 M = [HCOO-] [HCOOH] = 0.1 (
100 4.6 ) = 0.0954M 100

Example 2:

From the fact that acetic acid (CH3COOH) is 1.3 % ionized in 0.1 M aq solution, calculate the ionization constant of acetic acid and its percentage ionization in 0.2 M solution. What would be the hydrogen-ion concentration in a solution 0.10 M in acetic acid and containing sufficient dissolve acetate to give a total acetate-ion concentrated of 1.5M? Solution: CH3COOH H+ + CH3COOK CH 3COOH =

[ H + ][ CH 3 COO ] [CH 3 COOH ]

[0.0013][0.0013] = 1.8 x 10-5 [0.1 0.0013]

K CH 3COOH =

In 0.2 M solution CH3COOH H+ + CH3COO0.2 X X X

K CH 3COOH = 1.8 x 10-5 = [0.2 x ]
[ x ][ x ]

X = 1.9 x 10-3 M % ionization =

1.9 x 10 3 X 100 = 0.95% 0.2

For [CH3COO-] = 1.5 M

[ H + ][1.5] = 1.8 x 10-5 [0.1]

[H+] = 1.2 x 10-6 M

Dissociation Constant of Complex Ions An aqueous solution containing 0.1mol (=25g) CuSO4.5H2 is made ammoniacal (Cu+2 + 4Nh Cu (NH3)4+2) and is diluted o 500ml. The concentrated of dissolve NH3 in the resulting solution is found to be 1.5m. What is the molar concentrated of free cupric ions (Cu+2)? Dissipates constant Cu (NH3)4+2 = 4.5x10-14) Solution:

[Cu +2 ][ NH 3 ] [Cu ( NH 3 ) 4 ]
[Cu +2 ][1.5] [0.2]
4

+2

= 4.6 x 10-14

[Cu+2] = 1.8 x 10-15 M

= 4.6 x 10-4

Solubility Product (ksp) The solubility of calcium phosphate, Ca3 (PO4)2, in water is 2.5x10-5 g/ml. How many moles/liter does a standard solution of Ca3 (PO4)2 contain? How many grams of Ca are present in 500ml of the standard solution. Solution: MW Ca3(PO4)2 = 310
1 mole 1000 ml 2.5 x 10 5 g x x 310 g = 8.1 x 10-5 mol/L 1L ml

Ca3 (PO4)2 3Ca+2 + 2 PO4-2 (100% ionized) Ca3(PO4)2 = 3Ca+2 3(8.1 x 10-5) x (500/1000) = 1.2 x 10-4 mol Ca per 500 ml = 1.2 x 10-4(40) = 0.0048 g Ca 2. What is the solubility product of lead chloride of its solubility Hg per liter? What is the solubility of lead iodate of its solubility prod is 9.8x10-14? How many grams of lead can remain dissolve in 500ml of a solution which is 0.10m in iodate ions? Solution: PbCl2 Pb+2 + 2Cl[Pb+2][Cl-]2 = Ksp
11 g 11 = = 0.0396 M L 278

PbCl2 = 278

(0.0396)[(2)(0.0396)]2 = 2.5 x 10-4 Pb(IO3)2 Pb+2 + 2IO3[Pb+2][ IO3-]2 = 9.8 x 10-14

Let x = solubility of Pb(IO3)2 mol/L x (2x)2 = 9.8 x 10-14 x = 2.9 x 10-5 M = 1.6 x 10-2 g/L [Pb+2][ IO3-]2 = 9.8 x 10-14 [Pb+2][ 0.10]2 = 9.8 x 10-14 [Pb+2] = 9.8 x 10-12 mol/L = 1.0 x 10-9 per 500 ml (Please answer Chapter 6 problems pp.113 114 6.03 6.18) GNERAL PRINCIPLES OF GRAVIMETRIC ANALYSIS Principal Steps 1. Weighing of the sample 2. Dissolving the sample 3. Separation of some substance from solution containing 4. Isolation of that substance by filtration 5. determination of weight, by ignition Sample Problem 1. What is the percentage purity of sample KCIO3 which weighted 0.7440g and yielded precipitate of AgCl which weighed 0.5600g?
1 KCl KClO3 0.86 g AgCl x 1 ( AgCl ) x KCl _____________________________ x 100% = 98.67% 0.7440

2. What volume of 0.12M BaCl2 is required to precipitate the BaSO4 after the oxidation of sample of 0.1g of ore which is approximately 80% FeS2? Solution: FeSO4 + BaCl2 BaSO4 + FeCl2
2FeSO 4 2BaCl 2 1 mol ][ ][ ] BaCl 2 FeS 2 FeSO4 __________________________________ = 0.011125 L 0.12 mol/L 3. What weight of pyrite (FeS2) must be taken for analysis so that each milligram of precipitated BaSO4 shall represent 0.1% Sulfur is the sample

0.1(0.8g) [

Solution:

Let x = mass of the sample

S = BaSO 4 100 x
0.1

32 = 233 100 x
0.1

X = 137.3391 mg ore sample VOLUMERIC ANALYSIS / TRITIMETRIC ANALYSIS - involves measuring the volume of a solution of known concentration that is needed to react essentially completely with the analysis. Standard Solution (standard litrant) is a reagent of known concentrated that is used to carry out a titrimetric analysis. Titration a process wherein a standard so in is brought into reaction normally to neutralize the original solution. End pt point in titration where a physical change happens - refers to a experimental simation of equivalence point. Equivalence Point refers to the point when just enough tyrant has been added equivalent to the amount of analyze present. Titration Error the difference in volume of mass between equivalence point and the end point. Stoichiometric Reaction one in which definite, reproducible relationship exists between the reacting substances. Quantitative Reaction one the goes to completion when an amount of titrant equivalent to the amount of analyte present is added. Indicators often added to the analyte solution in order to give an observable physical change. Primary Standard a highly purified compound that serve as a reference material in all volumetric and mass titrimetric methods Important Requirements for a Primary Standard 1. High Purity 2. Stability towards air 3. Absence of hydrate water 4. Readily available to modest cost 5. Soluble water 6. Reasonable large molar mass Conditions for a Volumetric Mass

1. The reaction must be rapid and can be represented by a simple balance equation. 2. The reaction must be complete and no side reaction occurs. 3. An appropriate indicator must be available in order to detect the end point of the reaction. Types of Titration 1. Direct Titration the analyze reacts with the standard solution directly. 2. Back Titration an access standard solution is added and the excess is determined by the addition of other standard solution. 3. 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. Example: 1. Exactly 50ml of a solution containing 0.04m Cl is being titrated with a 0.05M AgNO3. Calculate the concentrated of Cl when titration is 70% complete, first neglecting and then include dilution. Assume that the reaction gos to completion. Repeat the calculations for a 0.50M AgNO3 titrant. Solution: a) Cl- + Ag+ AgCl(s) The amount of AgNO3 added is 70% of the amount of Cl- present Amt of AgNO3 added = amt Cl- x 0.7 = 50(0.04) mmol Cl- (0.7) = 1.40 mmol Amt of Cl- left = 50(0.04)mmol 1.4mmol = 0.6mmol Neglecting dilution [Cl-] =
0.6 mmol 50.00 ml

= 0.012 M

For dilution: Amt AgNO3 added = 1.40 mmol Vol AgNO3 = [Cl-] =
1.40 mmol 0.05 mmol / ml 0.06 mmol 50 +28.0ml

= 28.0 ml

= 0.0077 M = 2.8 ml

b) Neglecting Dilution; [Cl-] = 0.012 M After Dilution; vol AgNO3 = [Cl-] =

0.6 mmol 50 +2.80 ml 1.40 mmol 0.05 mmol / ml

= 0.011M

2. (Direct Titration Method) A 300g sample containing phosphoric acid and insert was diluted with water and titrated with 0.05M NaOH according to H3PO4 + 2NaOH Na2PHO4 + 2H2O. The end point was reached after 29.00ml of titrant was added. Calculate the % H3PO4 in the sample. Solution: % H3PO4 =
wt H 3 O4 x 100 = 23.68% wt smple

3. (Replacement or Indirect Titration Method) A 750mg sample of iron one was dissolve in acid and treated to oxidized all of iron to ferric ion. After destroying any remaining oxidizing agent, excess KL was added. The liberated I2 required 20.50ml of 0.07M Na2S2O3 for titration. What is the % Fe in the sample? Solution: 2Fe+2 + 2I- 2Fe+3 + I2 I2 + 2S2O3-2 2I- + S4O6-2 Amt. of Fe = 28.50 (0.075) mmol S2O3 [ = 119.3794 mg Fe+2 %Fe =
119.3794 x 100 = 15.92% 750
+3 -2

I2 2 S 2 O3
2

55.85 mol 2 Fe +3 ][ ][ 1 mol Fe +2 ] I2

3. (Back Titration) An 500mg sample of chromium ore was dissolve and the chromium oxidized to chromate ion. The solution was treated with 10.00ml of 0.20M AgNO3. The resulting ppt of Ag2CrO4 was removed and discarded. The excess AgNO3 required 14.50ml of 0.1200M KSCN for titration. Calculate the % Cr2O3 in the ore. Solution CrO4-2 + 2Ag+ Ag2CrO4(s) Ag+ + SCN- AgSN(s)
1CrO 4 % CrO3 = [ 10(0.2) 14.50(0.12) KSCN [ 1KSCN ][ 2 Ag
1Ag
2

1CrO 4 ][ 2 Ag

][ 1mmol ]

152 mg

X 100% (mg) 800mg % CrO3 = 9.88/800 x 100% = 1.24%

Examples: 1.To what volume must 1600ml of a 0.2050N solution be diluted in order that the resulting solution will be 0.2000N Solution: N1V1 = N2V2 (0.250) (1600) = (0.2000) V2 V2 = 1640 ml 2. How many milliliters of 0.3200N HCL must be added to 100ml of 0.1000N H2SO4 in order that the resulting solution will be 0.1200N as an acid? HCL + H2SO4 acid N1V1 + N2V2 = N3V3 (0.32) V1 + (0.1) (100) = 0.12 V3 V3 = 100 + V1 V1 = 10 ml 3. What is the normality of a solution containing 0.002892g of K2CO3 per milliliter? (b) What is the normality of the solution made by diluting 50.00ml of H2SO4 (spgr = 1.080 containing 11.60% H2SO4 by lit) to 1L with water? (c) how many milliliters of the carbonate solution will be completely neutralize by 7.00ml of the acid. Solution: a) N = fM N = 2[ 0.008292 b) N1V1 = N2V2 N1 = 1.080 ml x
g g 1000 ml L g ml

1000 ml L

1 mole 138 g

] = 0.12 N

1 mol 98 g

x 2 = 22.0408 N

Mass = 1.080 ml ( 0.1160 ) ( 50 ml ) = 6.624 g/L soln N = 6.624 L [

g 1 mol 98 g

] 2 = 0.1278 M

c) N1V1 = N2V2 ( 0.1200 ) V1 = ( 0.1278 ) ( 7.00 ) V1 = 7.46 ml Primary Standards for Bases: 1. Benzoic Acid C6H5COOH 2. Oxatic Acid H2C2O4 * 2H2O 3. Potassium Biiodrate KH(103)2 4. Potassium Hydrogen Phthalate (KHP) C6H4COOKCOOH

5. Sulfannic Acid (HSO3NH2) Primary Standards Acids 1. Calcium Carbonate, CnCO3 2. Mercuric Oxide, HGO 3. Sodium Carbonate, Na2CO3 4. Trishydroxymethylaminomethane THAM (CH2OH)3 COOH Exercises: About 10ml of concentrated HCL was transferred to a 1-L bottle and diluted with water. When this solution was use to titrate a sample of pure Na2CO3 weighing 0.3054g, it look 38.09ml to reach the methyl red end point. Calculate the molarity and left of the solution. For pH Calculations Sample: 1. When 0.02mole of a monoprotic acid is dissolved in 350ml of water, the pH=3.05. What is the ionization constant of this acid? Solution:
0.02 2 = M 0.35 35 1 3.05 = pH = log [ Ka] 3

[acid] =

HA

H+ + AX X

Ka = 1.4 x 10-5

Ka =

x2 Csa

x2 = Ka Csa
KaCsa

pH = -log

2. What mass in grams of NaC2H3O2 must be dissolved with 500ml of 0.100M acetic acid to make a 2L of buffer solution of pH=5? Ka=1.8x10-5 Solution of pH = 5? Ka = 1.8 x 10-5

500 ml 0.1M HAC, Ka = 1.8 x 10-5 pH = pKa log

[ acid ] [conj.base]

500 (0.1) mmol / 2 L (mg Na Ac) pH = - log[1.8 x 10 ] log [ ] 82mg ? mmol / 2 L

-5

mg Na Ac = -7380 = 7.38 g APPLICATION OF ACID-BASE-TITRATION Kjeldahl Method (Determination of Organic Nitrogen) 1. Step 1 Digestion the sample is oxidized in not, concentrated H2SO4 and turns back.

2. Step 2 Distillation the solution is cabled and then treated with NaOH to liberate ammonia gas. 3. Step 3 Titration Calculations: %N = VHCl MHCl [
[1N ] [1 NH 3 ] [14mg ] ][ ][ [1 mmol N ] ] x 100% [1 HCl ] [1 NH 3 ]

____________________________________________ Mass sample , mg

[1 HCL ]

%N = VHCl MHCl - VNaOH MNaOH [ [1 NaOH ] ][ 100%

[1N ] [1 NH 3 ] [14mg ] ][ ][ ]x [1 HCl ] [1 NH 3 ] [1 mmol N ]

___________________________________________________________________ Mass sample , mg % Protein = %N (f) f = 5.70 ( cereals) f = 6.25 ( meat products ) f = 6.38 ( dairy products )

2. Double Indicator Method: Mixture Na2CO3 and NaHCO3

CO3 -2 -------------------------------------------------------------------------

Vo Ph

HCO3- 1st end pt ----------HCO3- ---------------------------------------------------A B

Vo MR

CO2

CO2 2nd end pt -----------------------

Ph phenolphthalein MR Methyl/Red / Methyl orange (MO)

Solution Mg Na2CO3 = 2 (Vo ph) ( MHCl ) [ Mg NaHCO3 = (Vph MR - Vo

1 mmol Na 2 CO3 106.00 mg Na 2 CO3 2 mmol HCl x 1 mmol Na 2 CO3

ph

) ( MHCl ) [

84.01 mg NaHCO3 1 mmol NaHCO3 x ] 1 mmol HCl 1 mmol NaHCO3 84.01 mg NaHCO3 1 mmol NaHCO3 x 1 mmol HCl 1 mmol Na 2 CO3

Mg NaHCO3 = (Vph ]

MR

- 2Vo

ph

) ( MHCl ) [

Mixture of Na2CO3 and NaOH Solution: NaOH--------------CO3 -2 ------------------------------

Vo

Ph Vo MR

H2O

HCO3- 1st end pt ---------A Vph

MR

CO2 2nd end pt ----------1 mmol Na 2 CO3 106.00 mg Na 2 CO3 2 mmol HCl x 1 mmol Na 2 CO3 ] 1 mmol Na 2 CO3 106.00 mg Na 2 CO3 2 mmol HCl x 1 mmol Na 2 CO3
1 mmol NaOH
40.00 mg NaOH 1 mmol NaOH

Mg Na2CO3 = 2 (Vph Mg Na2CO3 = 2 (VMR

MR

) ( MHCl ) [ ) ( MHCl ) [

ph

Mg NaOH = (Vo ph - Vph Mg NaOH = (2Vo V0

MR

) ( MHCl ) [ 1 mmol HCl x ) ( MHCl ) [ 1 mmol HCl x

1 mmol HCl

] ]

40.00 mg NaOH 1 mmol NaOH

ph

MR

Relationship Between Sample Composition and Volumes of CHl Titrant to Reach Phenolphthalein and Methyl Red Point Sample Composition

PRECIPIMETERY - also called Argentometric Titration because AgNO3 is employed in such technique. - method in which a desired consistent is precipitated from solution by means of a standard solution of precipitating agent. - titration based on reaction produce sparingly soluble substances. - among the oldest titrations Applications: 1. Solubility Product the concentration of a dissolved solute at equilibrium with its undissolved form. Solution: AB aA + bB Ksp = [A]a [B]b AgCl Ag+ + Cl Ke =
[ Ag + ][Cl ] [ AgCl 5 ]

Ke = Ke [ AgCl(s)] = [ Ag+ ] [ Cl- ] Example: The solubility of Mg(OH)2 I 9.0x10-4g/100ml Compute Ksp value: Solution:
4 9.0 x 10 100 ml

= 9.0 x 10-3

g 1 mol [ 58 g ] = 1.55 x 10-4 M ml

[Mg+2] = 1.59 x 10-4 M ; [OH-] = 2 (1.55 x 10-4) = 3.10 x 10-4 Ksp = [Mg+2] [OH-]2 = (1.54 x 10-4) ( 3.10 x 10-4)2 = 1.49 x 10-11 2. Effects of Common Ions on Solubility Example: How many grams of AgCl ml dissolved in a liter of 0.01 MNaCl? Solution: NaCl Na + 0.001 Cl0.001 AgCl Ag+ + Cl0 0.01

S S ______________________ S S+0.01 Ksp = [Ag+] [Cl-] = 1 x 10-10 = (S) ( S+0.01) S = 10-8 M WAgCl = 143 x 10-8 g/l MWAgcl = 143

Example 2: Will a precipitate of AgCl be obtained when 3mg AgNO3 and 2mg NaCl are added o 250ml H2O? Solution:
3 2 mmol AgNO3 + mmol NaCl 170 58.453

[AgNO3] = 7.0588 x 10-5 M : [NaCl] = 1.3686 x 10-5 M Ksp = [7.0588 x 10-5 M] [1.3686 x 10-5 M] = 9.6607x 10-9 Ksp AgCl- = 1 x 10-10 ; precipitation will occur COMPLEXIMETRY - particularly used for the determinations cations - typical reagents used are organic compounds containing groups which are electron donors and have the ability to form multiple covalent bonds with th metal ions. A. Determination of Cyanide by th Liebig Method 2CN-1 + Ag+ Ag(CN)2-1 Ag(CN)2-1 + Ag+ Ag [ Ag(CN)2-1](s) endpt. Self indicating: ep = formation of permanent faint turbidity B. Determination of Nickel Addition of excess cyanide : Ni(NH3)2+6 + 4CN-1 + 6H2O Ni(CN)4-1 + 6N Back titration w/ Ag+ : 2CN-1 + Ag+1 Ag(CN)2-1 Endpt : Ag(CN)2-1 + Ag+ Ag [Ag(CN)2-1](s) C. Titration with EDTA (hexadentate) 4carboxyl groupsand 2amine MIn-1 + HY-3 HIn-2 + MY-2 Red blue D. Direct Tred Titration with added metal ions % - detn of Cat2

- small amount of MgCl2 is added to EDTA - Ca+2 replaces Mg+2 then bind with EBT to from red complex Example: A 2.00g sample of impure NaCN requires 24.95ml of 0.0500M AgNO3 solution to form a faint permanent turbidity. What is the % purity of th sampe? Given: 0.2g sample 24.95ml 0.05M AgNO3 Solution: Given: 0.2 grams sample 24.95 ml 0.05 M AgNO3 (24.95)(0.05) mmol AgNO3 [
1 mmol CN 2CN ][ 2 mmol CN ] AgNO3 Ag 122.255 mg NaCN = = 61.1275% 200 mg

Ag

][

2. A 500mg sample containing NaCN required 23.50ml of 0.1255M AgNO3 to obtain a permanent faint turbidity. Express the result of this analysis as % CNGiven: 500 mg sample NaCN 23.5 ml, 0.1255M, AgNO3 = (23.5)(0.1255) mmol AgNO3 [
Ag AgNO3

][

26mg 2CN ][ ] Ag 1CN

153.361 mg x 100 = 30.6722% 500

3. A solution is known of contain both KCl and KCN. A volume of 15.50ml of 0.1000M AgNO3 is required to give a faint permanent turbidity to he solution. A further addition of 25ml pipetful of the AgNO3 is made and the precipitate of the combined AgCl and Ag[Ag(N)2] is filtered off. The filtrate then requires 12.40ml of 0.05N KSCN to give are brown color with fern c ions. How many grams of KCl and of KCN were presnt in the sample. Solution: 15.50 ml 0.100 M AgNO3
KCN 65 mgKCN 2CN = (15.5)(0.1) mmol AgNO3 [ ][ ][ ][ ] AgNO3 Ag 1mmol 1CN
Ag

= 201.5 mg KCN For AgCl (25 ml 15.50 ml)(0.1) (12.4)(0.05) = 143.45

m

MAgCl = 47.3385 g [ m AgCl ] = 24.5685 mg KCl Determination of Nickel Example: A 750.25mg alloy of nickel was dissolved and treated to remove the impurities. The ammoniacal solution was treated with 50ml of a 0.1075M KSCN and the xss cyanide required 2.25ml of 0.00925M AgNO3. Det % Ni in the alloy. Solution: = [50 (0.1075) (5.25) (0.00925) [ =
78.2806mg x 100 = 10.43% 750.25
3 2 KCN 58.71 1Ni ( NH 3 ) 6 ][ ][1Ni][ ] 1AgNO3 1Ni 4CN

m KCl

Example 2: A alloy of nickel, free from interfering consistents an weighing 0.100g is dissolved in acid. The solution is made ammoniacal and is treated with 49.80ml of KCN solution, Ni(NH3)6+2 + 4CN-+6H2O ---- Ni(CN)4+6NH4OH. The xss cyanide is then titrated with 5.91ml of standard AgNO3 for a faint turbidiy, using KS as the indicator. The KCN solutions contains 7.810g KCN per liter, the AgNO3 solution contains 0.01699g AgNO3 per ml Calculate the % Ni in the alloy.
7.810 g 1mol [ 65 g ] = 0.1202 L 0.0169 g 1000ml 1mol N of AgNO3 = [ ][ 170 g ] = 0.0999N ml 1L

N of KCN =

2CN 58.71 1Ni ( NH 3 ) 6 [(49.80) (0.1202) (5.91) (0.0999) [ ][ ][1N][ ] AgNO3 1Ni 4CN

70.5275mg x 100 = 70.53% 100mg

TITRATION WITH EDTA AND DIRECT TITRATION W/ ADDED METAL ION Example 1. An EDTA soln prepared from its disodium salt was standardized using 506.3 mg of primary standard CaCO3 and consumed 28.50 ml of the soln. The standard soln was used to determine the hardness of a 2L sample of mineral water, w/c reqd 35.57 ml EDTA soln. Express the analysis in terms of ppm CaCO3.
506.3mg CaCO3 x 35.57 ml EDTA / 2L = 315.9490 28.50ml EDTA

2. What volume of 0.0305 M EDTA is needed to titrate Ca in 178.56 mg of CaCO3?

(vol EDTA) (0.0305) mmol EDTA = Vol EDTA = 58.5543 ml

MCaCO3 = 178.56 mg 100 mg / mmol

3. A 100 ml aliquout of only drinking water was treated w/ a small amt. of an ammonia ammonium chloride buffer to bring the pH to 10. After the addition of (Ca Inagite) indicator, the solution equation 21.46 ml of 5.140 x 10-3 M EDTA for titration. Calculate the water hardness in terms of ppm CaCO3.
1CaCO3 100mg ][ ] 1EDTA 1mmol ____________________________________________________ = 110.3044; 110 ppm

= (21.46)(5.140 x 10-3) mmol EDTA [

1L 1000ml

100 ml x

(Neutralization) 1. Calc. the solution during titration 50 ml of 0.05 M of NaCl w/ 0.1 M AgNO3 after the addition of the ff. volumes of the reagent (a) 0.00 ml (b) 24.5 ml (c) 25 ml (d) 25.5 ml 2. The arsenin in a 9.13g sample residue was converted to ASO4-3 and precipitated as Ag3ASO4 w/ 50 ml of 0.02105 M of AgNO3. The excess Ag+ was titrated w/ a 4.25 ml of 0.04321 M KSCN, Calculate the % AS2O3 in the sample. (50) (0.02125) (4.75) ( 0.04321) = AS2O3 = 2 AsO4-3 = 6 AgNO3
(0.8023 AgNO3 )( 1AS 2 O3 AS 2 O3 ) )(0.1984 g )( 6 AgNO3 mmol = 0.2906 9.13 g sample

3. A mixture of LiCl and BaBr2 weighing 0.5g is treated w/ 37.6 ml of AgNO3, and the excess of the latter requires 18.50 ml of KSCN solution for titration, find the % of Cl in the mixture. mLiCl + m BaBr2 = 0.5g 0.2 N, 37.6 ml AgNO3 18.5 ml of 1/9 N KSCN For Titration

m BaBr2 = 0.5 m LiCl

mBaBr2 mLiCl 1AgNo3 + = mol AgNO3 mol KSCN [ ] MW / f MW / f 1KSCN

x 0 .5 x + = (0.2)(0.0376) (1/9)(0.0185) 42.5 / 1 297 / 2

X = m LiCl = 0.1247g m BaBr2 = 0.3753g % = 0.1247g [

35.45 ] / 0.5 x 100% = 20.82% 42.45

What is the normality of a solution of KSCN, and how many grams of KSCN are contained in each liter of 19.80 ml are required to titrate the silver in a 0.1 g sample of an alloy w/c contains 90.20% Ag & 9.80% Cu2.
19.8 ml [ mmol Ag ][ ] ml 1000 = 0.9020 0.1
97 g ] = 4.0934 g 1mol

NKSCN = 0.0422 N 0.0422 N [

A sample of iron ore weighing 385.8 mg was dissolved in acid and pass through a Jones redactor. If the resulting solution requires 52.36 ml of 0.01436 M K2Cr2O7 for titration, calculate the % Fe3O4 and Fe2O3 in the sample. 52.36 ml, 0.01436 K2Cr2O7
(6)(52.36)(0.01436) m = 55.81 / 1 1000

mFe = 0.251958205 g mFe3O4 = 0.251958205 [ %Fe3O4 =

1Fe3 O4 ] = 0.3482 3Fe

0.3482 x 100 = 90.30% 0.3856

A mixture of LiCl & BaBr2 weighing 0.6g is treated 45.15 ml of 0.2017 N AgNO3, and the excess is found to require 25 ml of 0.1 N KSCN solution for the titration using ferric aluminum as indicator. What is the % of BaBr2 in the sample? LiCl + BaBr2 = 0.6g mBaBr2 = 0.6 mLiCl

( 45.15)(0.2017) ( 25)(0.1) mLiCl 0.6 mLiCl = + 42.45 297 / 2 1000

mLiCl = 0.1525 g mBaBr2 = 0.4475 g % BaBr2 = 74.58 % COMPLEX FORMATION TITRATION Ligand donor species Coordination Number the number of covalent bonds that a cation tends to form w/ electron donors Chelates particular class coordination - produced when a metal ion coordinates w/ two or more donor groups of a single ligand to form a five or six membered heterocyclic ring Problem Calculate of equilibrium concentrate of Ni+2 in a solution with an analytical NiY2 conc. Of 0.0150 M at pH (a) 3.0 (b) 8.0 Ni+2 + Y+4 NiY2KMY =
[ NiY 2 ] = 4.2 x 1018 [ Ni +2 ][Y 4 ]

[NiY2-] = 0.0150 [Ni+2] If we assume [Ni+2] <<< 0.0150 NiY-2 = 0.0150 [Ni+2] = CT = [Y-4] + [HY-3] + [H2Y-2] + [H3Y-1] + [H4Y] KMY =

4 KMY =

= 2.5 x 10-11
0.0150 = [ Ni +2 ] 2

[ NiY 2 ] [ NiY 2 ] = [ Ni +2 ] 2 [ Ni +2 ]CT @ pH 3.0

KMY = 2.5 x 10-11 x 4.2 x 1018 = 1.05 x 108

10 1.43 x10

[Ni+2] =

0.0150 = 1.05 x10 8

= 1.2 x 10-5 M

@ pH 8 KMY = 5.4 x 10-3 (4.2 x 1018) = 2.27 x 1016 [Ni+2] =

0.0150 = 8.1 x 10-10 M 16 2.27 x10

Volumetric analysis Analysis of samples All titremetric analysis require the ff. steps 1. Preparation of sample solution. 2. Titration of the sample solution The solution is titrated by a standard solution of the reagent The titration may be made either to (a) a dead stop endpoint or (b) past the end pt, followed by back titration w/ sample soln or another std soln. 3. Computations can be express in (a) molarity or normality of the solution (b) weight of the given substance present (c) percentage of the given constituent sample Sources of Error in Titremetric Operations 1. Loss of sample or solution by spilling in weighing, spilling solution as it transfers, leaking burets, faulty piping, etc. 2. Contamination on solution by failure to properly rinse burets, pipets and bottles. 3. Faulty mixing of solutions after they have been diluted. 4. Impurities in the primary standard in w/c the concentration values are based. 5. Errors in weighing 6. Errors in reading burrets. 7. The use of wrong indicators for titrations 8. Poor drainage from buret or pipet because application has not been cleaned. Neutralization Method Standard Solution - usually solutions of strong acids or bases. Bases, however, are not as good as acids for permanent std because they absorb CO2 whenever they come in contact in air. - Also reacts with glass on long storage - Can be stored in pyrex or plastic bottles For many purposes it is desirable to remove the carbonate when preparing standard solutions of bases. The prescence of carbonate ions interferes with some titrations by so buffering the solution that the endpoint is not sharp.

The carbonate can be sufficiently removed either by precipitation as BaCO3 or by initially making a saturated solution of sodium hydroxide, in w/c sodium carbonate has a fairly ion solubility and filtering out the carbonate before diluting the desired strength Standardization KHP phenolphthalein carbonate free strong bases Gravimetric Standardization if no primary std. reagent is available, acid base soln may be standardized by determining the chloride ion of a hydrochloric acid solution gravimetrically. Other standards 1. Tris ( Hydroxymethyl) aminomethane ( CH2OH)3CNH2 - non hygroscopic ( THAM ) 2. Calcite 3. Sulfamic Acid ( HNH2SO3) Acid Base Indicators - in all neutralization titrations, result are dependent on the selection of the proper indicator Indicators used in Neutralization Titrations - highly colored organic compounds - change color when [ H+] of the solution is changed over a certain range. Most Widely Used 1. Phenolpthalein colorless [H+] > 10-8 pink [H+] < 10-15 2. Methyl Orange 3. Methyl Red 4. Brom cresol green #22. 265(P) A 9.05 NH3 solution is treated w/ 50 ml 0.4982 N H2SO4 ; 21.64 ml 0.1016 N NaOH is required for back titration. What is the percentage of NH3 in the solution? [50(.4982) (21.64)(.1016) meq NaOH x
17 mg 1 meq NH 3

1 meq NH 3 1 meq H 2 SO4 ][ ][ 1 meq NaOH 1 meq H 2 SO4

x 100% 9050 mg = 4.27%

*note: in equivalence : all are equal not to be confused with mmols as units

#23/265 (P) 44.50 ml 0.2020 NaOH is required to neutralized a 0.5g sample of a crystalline organic acid. What is the equivalent weight of the acid? If the acid is dibasic and completely neutralized in the titration, how many grams of it are required to prepare 300 ml 0.40 M solution? 45.50 ml 0.2020 N NaOH = 0.50 g organic acid (a) g equivalent weight (b) g of acid for preparation of 300ml 0.4M solution if it is treated

g solute
N = g eq weight x
meq ml

1 L

0.2020

500 mg g eq weight

1 45.50ml
500

(a) g equivalent weight = (b) f =2 MW = ?

(0.2020)( 45.50)

= 54.4010 mg/meq

g eq wt = MW/f 54.4010 = MW = 108.802089 mg/mmol 0.4

MW 2 meq / mmol

mmol (300ml) = 120 mmol ml

108.802089 mg/mmol (120 mmol) = 13056.25068 mg = 13.0563 g of organic acid #23/265 (P) The saponification number of a fat or oil is defined as a number of milligrams of KOH required to saponify 1g of fat or oil. To a sample of butter weighing 2.010g is added 25ml 0.4900 N KOH solution. After saponification is complete, 8.13 ml 0.5 N HCl is found to required to neutralize the excess alkali. What is the saponification number of butter. [25(0.49) 8.13(0.5)] 56 mg ________________________ = 228.04 2.10 g #28/266(P) To what volume must 50 ml conc. nitric acid, d = 1.4450 g/ml containing 78% HNO3 by weight, be diluted to contain 10g HNO3 per 100 ml (10 W/V %)

78 g HNO3 100 g solution

1.445 g so ln ml solution

] 50ml =

10 g (vol 2 ) 100 ml

V2 = 563.55 ml TITRATION WITH 2 INDICATORS The existence of two breaks in the titration curves of polyprotic acids or their salts permits simultaneous determination of two constituent of sample mixtures, by a single titration employing two separate indicators to give separate end pt. Solution containing NaOH & Na2CO3 - titrated by HCl to ph end pt. - amt of acid used = amt of OH- + amt that reqd to convert CO3-2 to HCO3- volume of the acid is noted - then Mo turning at pH 4 5 is added - continued to reach the second end pt. is required to convert HCO3- to CO2 Ex. It is found that 15.00 ml 0.100 N HCl titrates a sample containing both NaOH and Na2CO3 to pH end pt. an additional 10 ml of acid is required to continue the titration to MO EP. Compute the weights of NaOH of Na2CO3 in the sample. Total vol of HCl used = 15 + 10 = 25ml 25 (0.100) = 2.5 meq 10 ml @ 1.0 meq HCO-3 CO2 and H2O then 10 ml @ 1.0 meq CO3-2 HCO3Total meq used by the carbonate = 2.0 meq Wt. of Na2CO3 = 2.0 (53 mg/meq) = 106.00 mg Na2CO3 Since 2.0 meq HCl was used to titrate the carbonate, the amount of HCl used for NaOH = 2.5 2.00 = 0.5 meq 0.5 meq (40 mg/meq) = 20 mg NaOH OXIDATION REDUCTION ANALYSIS Two types of reactions in aquaeous solution 1. Metathesis or double decomposition (precipitation & neutralization) 2. Oxidation Reduction ( change in oxidation states ) Gaining of electrons reduced

Losing of Electrons oxidized Ce+4 + Fe+2 Ce+3 + Fe+3 1e - + Ce+4 Ce+3 Fe+2 Fe+3 + 1eO.A R.A

REDOX reaction may be used as a basis for a volumetric analysis if 1. There is only one reaction under given condition 2. This reaction goes essentially to completion at the equivalence pt. 3. Suitable indicator ( or other means ) is available to locate the endpt. 3 Categories in the General Methods of Redox Analysis 1. A solution of a substance that really oxidized is titrated by a std. soln of strong oxidizing agent (SOA) Most wildly used strong O.A. (a) MnO4- in acidic solution (b) Cr2O7-2 in acidic solution (c) Ce+4 in acidic solution (d) I2 in I- solution (e) MnO4- in basic solution In titrations of reducing agents by a strong oxidizing agent, it is necessary to pre-treat the sample before the titration, to ensure that all the sought subs. Is reduced to its lower oxidation state to insure that no reducing agent other than the sought material is in the solution. For example, Fe 2Fe+2 + Zn 2 Fe+2 + Zn+2 After reduction, metallic zinc is removed from the solution, then titrated by a standard solution of KMnO4 : MnO4- + 5e+2 + 8H+ Mn+2 + 5e+2 + 4H20 2. If the sample is SOA, it mat be analyzed by titrating the solution w/in a solution of a reducing agent. Most widely used red agents (a) Ferrous Salt solution (b) Arsenious Acid * Samples of Oxidizing Agents that are not water soluble may be analyzed by treating a known weight of sample w/ a measured volume of standard Reducing Agent, and after the reaction is complete, back-titrating the excess of the reducing agent in the solution with a std soln of an oxidizing agent.Thus, the amount of MnO2 in a sample is determined by treating a weighed portion with a measured volume of standard. FeSO4 solution and back titrating the xss with a standard KMnO4 solution.

3. An indirect method is frequently used for analysis of oxidizing agents. The sample is treated with a solution of KI, and liberated iodine is titrated by a solution of Na2S2O3 w/c reacts rapidly and quantitatively with I2. I2 + S2O3-2 2I- + S4O6-2 3 Standard Reagents 1. KMnO4 strong OA 2. H3AsO3 strong RA 3. Na2SO3 specific reagent for I2 Indicatots for Redox Titrations - the indicator must be a substance that is oxidized or reduced at or near the equivalence point of titration. For Titrating a Reducing Agent - indicator must be a substance that is more difficult to oxidized than the sample Two most widely used 1. Diphenylamine Sulfonic Acid ( normally used as the soluble barium or sodium salt) - strong RA used for Cr2O7-2 2. Ferrous Complex or Orthophenanthroline ( Ferrom) - strong OA for KMnO4, CeSO4 More Common Specific Redox Indicators 1. Color of the permanganate ion - When the reduced MnO4 gives (in acid solution) the colorless Mn+2 - The colored endpt. Appears with the first drop of MnO4- in xss, after all the sample is oxidized 2. Starch Indicator for I2 - colloidal suspension of starch will, in the prescence of I-, give an intense blue color with free I2 3. Spot Test Indicator - made as the equivalent pt is approached - done by withdrawing a drop of solution after each addition of each reagent and testing this drop for the constituent that is being oxidized or reduced 4. Potentiometric Endpoint - voltage difference Oxidation Reduction Equations First step in balancing equation is to know the products formed in the reaction. Common Oxidizing Agents and their products

Reactant MnO4- + H+ Cr2O7-2 + H+ Ce+4 ClO3- + H+ BrO3- + H+ IO3+ + H+ NO3- + H+ H2O2 + H+ MnO2(s) + H+ PbO2(s) + H+ Fe+3

Medium Acid Acid ` Acid Acid Acid Acid Acid Acid Acid Acid Acid

Products Mn+2 + H2O Cr+3 + H2O Ce+3 Cl- + H2O Br- + H2O I- + H2O NO + H2O H2O Mn+2 + H2O Pb+2 + H2O Fe+2 Products NO3- + H+ I2 CO2 S(s) + H+ SO4-2 + H+ H3ASO4 + H+ S4O6-2 Fe+3 Sn+2 Zn+2

Common Reducing Agents and their Products Reactant Medium HNO2 +H2O Acid IAcid or neutral C2O4-2 Acid H2S Acid SO2 + H2O Acid H3ASO3 + H2O Acid or neutral S2O3-2 Acid or neutral +2 Fe Acid Sn+2 Acid Zn(s) Acid Example 1 MnO4- + H+ Mn+2 + H2O 1. Write the half reaction for O.A. 2. Balance half rxn MnO4- + 8H+ Mn+2 + 4H2O 3. Balance the charge Mn+7 + 5e- Mn+2 MnO4- + 8H+ + 5e- Mn+2 + 4H2O 4. Write the half reaction for R.A. Fe+2 Fe+3 + 1e5. Balance the electron in two half rxn (MnO4- + 8H+ + 5e- Mn+2 + 4H2O) 1 (Fe+2 Fe+3 + 1e-) 5 MnO4- + 8H+ + 5e- Mn+2 + 4H2O 5Fe+2 5Fe+3 + 5e-

6. Add the 2 half rxn MnO4- + 8H+ + 5Fe+2 Mn+2 + 4H2O + 5Fe+3 In molecular state form KMnO4- + 4H2SO4 + 5FeSO4 MnSO4 + 4H2O + 2.5Fe2(SO4)3 + 0.5 K2SO4 Or 2KMnO4- + 8H2SO4 + 10FeSO4 2MnSO4 + 8H2O + 5Fe2(SO4)3 + K2SO4 Cr2O7-2 + 14H+ + 6e- 2Cr+3 + H2O ( H2S S + 2H+ 2e- ) 3 Cr2O7-2 + 8H+ + 3e- 2Cr+3 + 7H2O + 3S K2Cr2O7-2 + 4H2SO4 + 3H2S Cr2(SO4)3 + 7H2O + 3S + K2SO4 Typical Calculations A. Preparation of reagent g eq wt = # of electron gained + lost
MW

1. What weight of pure K2Cr2O7 is needed for the preparation of 500 ml 0.1 N solution?
K2Cr2O7 = 294.21/6 = 49.04 g/eq 6e meq= 49.04 mg

g eq wt =

500 (0.1) = 50 meq 50 (49.04) = 2452 mg or 2.452 g B. Standardization of reagent 1. A solution of KMnO4 is standardized by comparison with Na2C2O4. From the ff. data, calculate the N of KMnO4. Wt of MnO4- = 40.41 ml Wt of Na2C2O4 = 0.2538 g Purity of oxalate = 99.60% C2O4-2 2CO2 + 2eg eq wt of Na2C2O4 = 0.5 mole f=2 wt of pure Na2C2O4 = 0.996 (0.2538) = 252.8 mg

g eq wt of Na2C2O4 = 134/2 = 67 mg/meq meq of Na2C2O4 = meq KMnO4 =252.8 mg [ 67 mg ] = 3.773 meq Normality KMnO4 =
3.773 meq = 0.0934 N 40.41ml
1 meq

C. Analysis of sample A sample contg iron is dissolve, all iron is reduced to ferrous condition and the resulting solution is titrated with std KMnO4 solution. From the ff. data, calc the % iron, as Fe2O3 in the sample.

Wt of the sample = 1.097 mg Vol KMnO4 = 37.63 ml N of KMnO4 = 0.1050 N meq Fe = meq KMnO4 = 37.63 ml [ g eq wt. Fe2O3 = wt Fe2O3
159.70 mg 2meq 79.85 mg = [ meq ] (3.951

0.1050meq ] = 3.951 meq ml

meq) = 315.4 mg

% Fe2O3 =

0.3154 x 100 = 28.75% 1.097

D. Indirect Oxidation Titration A solution of KMnO4 is 0.10 N; 40ml of this solution is added to an acidified solution w/c contains excess KI. The I2 liberated is titrated by 35.00 ml Na2S2O3 solution. What is the normality of Na2S2O3? 2MnO4- + 16H + 10I 2Mn+2 + 5I2 + H2O I2 + 2S2O3-2 S4O6-2 + 2Imeq of KMnO4 = 40 (0.1) = 4 meq = meq I2 = meq Na2S2O3 NNa2S203 = 4 meq/ 35 ml = 0.1143 N Sample Prob. #8. How many grams of AS2O3 must be dissolved in conc. NaOH to produce 500 ml 0.05 N NaASO2.

500 (0.05) meq [ 4meq ] = 1237.5 mg #11 How many ml of 0.0973 N K2Cr2O7 solution are reqd to titrate a 0.3563 g sample of an iron ore w/c is 78.33% Fe2O3?

198mg

Volumetric Analysis by precipitation Recall: Determination can be made by volumetric methods if 1. 2. 3. 4. The reaction goes rapidly to completion There is only one reaction There is a marked change in some property of the solution at the equivalence pt. An indicator is available w/c will show the change at the equivalence pt. most precipitation reaction fulfill three requirements since they are ironic no indicators are available for most precipitation reactions

Indicators 1. Formation of colored ppt. - best known example is the use of silverchromate as indicator in the titration of chloride with silver nitrate solution - known as the Mohr Method 2. Formation of soluble colored compound Volhard Method - solution contg Ag ion are titrated with std soln of KSCN. Ag + SCN- AgSCN ( white ppt) When the equivalence is passed, the concentration of thiocyanate increases to such an extent that the ion may be detected by means of reaction Fe+3 +6SCN- Fe (SCN)6-3 (colored) Ferric aluminum is usually employed as indicator Titration may be made in nitric acid solution 3. Absorption Indicators Fajans et al. shown that certain organic dyes may be used as indicators for volumetric precipitations reactions. The action of these indicators is due to fact that the equivalence pt. the indicator is absorbed by the precipitate.

The theory of the action of the absorption indicators is based on the properties of colloids. At the surface of the colloidal particle is a layer of that ion of the lattice w/c predominate in the surrounding solution. This primarily absorbed layer hold by secondary absorption oppositely charged ions w/c are present in the solution. The ion w/c is most strongly held by secondary absorption is the ion of the solution whose compound w/ the primarily absorbed ion in least soluble. Flourescein or dichlorofluorescein may be used as absorption indicators in titration of chlorides by silver ion. Before the equivalence pointis reached, the primary absorption is one of chloride ion, the lattice in excess. Just at the equivalence point silver ion is absorbed, giving a positively charged particles w/c can hold negatively charged fluorescein ions by secondary absorption. When this occurs, the structure of the fluorescein ion is changed to for a colored substance that coats the particle. Succesful use of absorption indicators requires the following conditions 1. The indicator ion must be of opposite charge to the ion used for titration reagent. 2. The indicator must be specifically absorbed to such extent that the color change appears immediately after the equivalence point. 3. the indicator must not be strongly absorbed by the precipitation. If this occurs, the absorption of the indicator may be a primary reverse w/c takes place before the equivalence point is reached. 4. The ppt formed should remain highly dispersed. Since the color changes occurs only at the surface precipitated particles, the visibility of the changed depends on the number of particles. Partial list of Absorption Indicators for volumetric Titration ClBr ISCNCNAg+ OHBO2B4O7-2 SO4-2 Titration ion Ag+ Ag+ Ag+ Ag+ Ag+ BrPb+2 Pb+2 Pb+2 Indicator Dichlorofluorescein Eosin Eosin Eosin Diphenyl carbazide Rhodamine Fluorescein Dichlorofluorescein Notes ph > 4 ph > 2

In 0.5 N HNO3 Quitesharp in 0.01 and 0.1 N Solutions Accurate in neutral solution

Dibromofluorescein A better method is based on fractional precipation

Quiz No.3 Precipitimetry and Compleximetry

Compleximetry 1. What is Compleximetry? 2. Cite instances/examples where compleximetry is being utilized? Choose one application and explain how the analysis is done. 3. Discuss the theory of complexation of indicators. Explain the mechanism. Precipitimetry 1. Discuss the precipitimetry. What are the factors to be considered in a precipitimetric analysis? Explain each. 2. Discuss all the methods in precipitimetry. Cite each process, how it is done and the advantages and disadvantages. Tabulate your result. 3. How is the equivalence point is achieved in precipitimetry and the factors the shape of titration curve. Chem 351 Analytcal Chemistry Laboratory Comprehensive Examination Objectives 1. To be able to develop and apply knowledge in analytical chemistry lectures. 2. To be familiar with the principles and procedures in the preparation and standardization of reagents. 3. To enhance the critical thinking skills of students in the application of principles and knowledge gained. General Direction : Answer all the following items using your knowledge gained in Anal Chem Laboratory. Several principles and theories can be recalled / used from your general chemistry and engineering sciences.