Analytical Chemistry Gas Tests

Gas Preparation and Tests

Gas Example of Preparation Decomposition of hydrogen peroxide Oxygen (O2) H2O2 -----> H2O + O2(g) Ignites a glowing splint since oxygen supports combustion Test

Thermal decomposition of some metallic oxides 2PbO -----> 2Pb + O2(g) acid + metal -----> salt + hydrogen gas Hydrogen (H2) 2HCl + Zn -----> ZnCl2 + H2(g) "Pop Test" : a lit taper will produce an audible "pop" when placed in hydrogen gas

active metal + water -----> hydroxide + hydrogen gas Ca(s)+ 2H2O--->Ca(OH)2+ H2(g) acid + carbonate -----> salt + water + carbon dioxide Carbon dioxide (CO2) 2HCl+CaCO3->CaCl2+H2O+CO2(g)

When CO2(g) is bubbled through colourless limewater (Ca(OH)2(aq))the limewater turns milky due to the formation of a calcium carbonate (CaCO3(s)) precipitate. When CO2(g) is bubbled through Ba(OH)2(aq) a white precipitate of BaCO3 forms.

Thermal decomposition of some carbonates CuCO3 -----> CuO + CO2(g) Nitrogen dioxide (NO2) Thermal decomposition of some nitrates 2Ni(NO3)2--->2NiO + O2+

Nitrogen dioxide is a red-brown gas which is soluble in water and has a pungent odour.

4NO2(g) 2Pb(NO3)2--->2PbO + O2+4NO2(g)

Less active metals + nitric acid -----> nitrate + water + nitrogen dioxide Cu + 4HNO3 ---> Cu(NO3)2 + 2H2O + 2NO2(g) Combustion of sulfur S(s) + O2 -----> SO2(g) SO2(g) is bubbled through hydrogen peroxide solution (H2O2) to produce sulfuric acid (H2SO4). The addition of barium chloride solution (BaCl2(aq)) to this solution results in aprecipitate of barium sulfate (BaSO4(s)). SO2(g) passed through a concentrated, acidified solution of potassium dichromate (K2Cr2O7) causes the dichromate solution to change colour from orange to green due to the formation of chromium (III) ions (Cr3+).

Sulfur dioxide (SO2)

Sulfites + acid -----> water + sulfur dioxide SO32- + 2H+ -----> H2 + SO2(g)

Hot concentrated sulfuric acid + copper 3H2SO4 + Cu(s) --->Cu2++2HSO4-+2H2O +SO2(g)

H2S is often referred to as "rotten egg gas" as it smells just like rotten eggs! sulfide + acid -----> salt + Hydrogen hydrogen sulfide sulfide (H2S) FeS(s) + 2HCl ---> FeCl2 + H2S(g) H2S(g) is passed through a solution of zinc chloride (ZnCl2) and a white precipitate of zinc sulfide forms (ZnS(s)). Pass H2S(g) over a damp filter paper impregnated with lead (II) nitrate (Pb(NO3)2), the paper turns black as lead (II) sulfide (PbS(s)) forms. Cl2(g) is a pale yellow-green gas which bleaches coloured materials and has a characteristic choking odour.

Chlorine (Cl2)

MnO2(s) + 2Cl- + 4H+ --->Mn2+ + 2H2O + Cl2(g)

Electrolysis of molten sodium

chloride (NaCl) 2NaCl -----> 2Na(Hg) + Cl2(g)

(Na(Hg) is a mercury amalgam of sodium metal since sodium is slightly soluble in mercury but doesn't react with mercury as it does with other solvents like water.)

Gravimetric Analysis

Rules for Learning the Solubility of Ionic Compounds in Water

Negative Ions (Anions) any anion + Positive Ions (Cations) alkali ions (Li+,Na+,K+,Rb+,Cs+,Fr+) hydrogen ion [H+(aq)] Solubility of = compounds in water = soluble Example

sodium fluoride, NaF, is soluble hydrogen chloride, HCl, is soluble ammonium chloride, NH4Cl, is soluble potassium nitrate, KNO3, is soluble sodium acetate, CH3COONa, is soluble silver chloride, AgCl, forms a white precipitate (a white solid) potassium bromide, KBr, is

any anion

soluble

any anion

amonium ion (NH4+)

soluble

nitrate NO3-

any cation

soluble

acetate (CH3COO-)

any cation

soluble

Chloride (Cl-), Bromide (Br-), + Iodide (I-)

silver (Ag+), lead (Pb2+), mercury (Hg2+), copper (Cu+), thallium (Tl+)

low solubility (insoluble)

any other cation

soluble

soluble barium sulphate, BaSO4, forms a white precipitate (a white solid) copper sulphate, CuSO4, is soluble magnesium sulfide, MgS, is soluble zinc sulfide, ZnS, is insoluble strontium hydroxide, Sr(OH)2, is soluble silver hydroxide, AgOH, is insoluble (forms a precipitate) ammonium phosphate, (NH4)3PO4, is soluble magnesium carbonate, MgCO3, is insoluble

+ Sulphate (SO42-) +

calcium (Ca2+), strontium (Sr2+), barium (Ba2+), silver (Ag+), lead (Pb2+), radium (Ra2+)

low solubility (insoluble)

any other cation

soluble

+ Sulfide S2+

alkali ions (Li+,Na+,K+,Rb+,Cs+,Fr+), alkali earth metals (Be2+,Mg2+,Ca2+,Sr2+,Ba2+,Ra2+), and H+(aq), NH4+ any other cation

soluble

low solubility (insoluble)

+ Hydroxide OH+

alkali ions (Li+,Na+,K+,Rb+,Cs+,Fr+), H+(aq),NH4+,Sr2+,Ba2+,Ra2+,Tl+

soluble

any other cation

low solubility (insoluble)

Phosphate, PO43-, Carbonate, CO32-, sulphite, SO32-

alkali ions (Li+,Na+,K+,Rb+,Cs+,Fr+), H+(aq),NH4+

soluble

any other cation

low solubility (insoluble)

All compounds of the ammonium ion (NH4+), and of Alkali metal (Group IA) cations, aresoluble. All nitrates and acetates (ethanoates) are soluble. All chlorides, bromides and iodides are soluble EXCEPT those of silver, lead and mercury(I).

All sulphates are soluble EXCEPT those of silver, lead, mercury(I), barium, strontium and calcium. All carbonates, sulfites and phosphates are insoluble EXCEPT those of ammonium and Alkali metal (Group IA) cations. All hydroxides are insoluble EXCEPT those of ammonium, barium and alkali metal (Group I) cations. All sulfides are insoluble EXCEPT those of ammonium, Alkali metal (Group I) cations and Alkali earth metal (Group II) cations. All oxides are insoluble EXCEPT those of calcium, barium and Alkali metal (Group I) cations; these soluble ones actually react with the water to form hydroxides (hydrolyse).

Gravimetric Analysis
Key Concepts i. ii. iii. iv. v. vi. vii. viii. ix. the air Gravimetric analysis is the quantitative isolation of a substance by precipitation and weighing of the precipitate. An analyte is the substance to be analysed. A precipitating reagent is the reactant used to precipitate the analyte. Procedure: Weigh the sample to be analysed Dissolve the sample in a suitable solvent, eg, water Add an excess of the precipitating reagent to precipitate the analyte Filter the mixture to separate the precipitate from the solution Wash the precipitate to remove any impurities Dry the precipitate by heating to remove water Cool the precipitate in a dessicator to prevent the precipitate absorbing moisture from Weigh the cooled precipitate Repeat the drying and weighing process until a constant mass for the precipitate is achieved Calculate the percent by mass of analyte in the sample

x.

General calculation of the percent by mass of analyte in a sample: Wite the balanced chemical equation for the precipitation reaction Calculate the moles of precipitate: moles = mass molecular mass

1. 2.

3. Calculate moles of analyte from the balanced chemical equation using the mole ratio of analyte : precipitate 4. 5. Calculate mass of analyte: mass = moles x molecular mass Calculate percent by mass of analyte in sample: (mass analyte mass sample) x 100 Sources of Error:

a. Incomplete precipitation results in a value for the percentage of analyte in the sample that is too low. b. Incomplete drying of the sample results in a value for the percentage of analyte in the sample that is too high c. Other ions in the sample may also be precipitated resulting in a value for the percentage of analyte in the sample that is too high Example A 2.00g sample of limestone was dissolved in hydrochloric acid and all the calcium present in the sample was converted to Ca2+(aq). Excess ammonium oxalate solution, (NH4)2C2O4(aq), was added to the solution to precipitate the calcium ions as calcium oxalate, CaC2O4(s). The precipitate was filtered, dried and weighed to a constant mass of 2.43g. Determine the percentage by mass of calcium in the limestone sample. 1. Wite the balanced chemical equation for the precipitation reaction: Ca2+(aq) + C2O42-(aq) -----> CaC2O4(s) 2. Calculate the moles of calcium oxalate precipitated. n(CaC2O4(s)) = mass MM n(CaC2O4(s)) = 2.43 (40.08 + 2 x 12.01 + 4 x 16.00) n(CaC2O4(s)) = 2.43 128.04 n(CaC2O4(s)) = 0.019 mol

3.

Find the moles of Ca2+(aq). From the balanced chemical equation, the mole ratio of Ca2+ : CaC2O4(s) is 1 : 1 So, n(Ca2+(aq)) = n(CaC2O4(s)) = 0.019mol

4.

Calculate the mass of calcium in grams mass (Ca) = n x MM mass (Ca) = 0.019 x 40.08 = 0.76g

5.

Calculate the percentage by mass of calcium in the original sample: %Ca = (mass Ca mass sample) x 100 %Ca = (0.76 2.00) x 100 = 38%

Acids and Bases

Definitions and Properties of Acids and Bases

ACIDS Examples BASES

Mineral Acids: hydrochloric acid,HCl cleaning metals and mortar, used in swimming pools to adjust pH, found in stomach sulfuric acid, H2SO4 used in car batteries, used to make fertilizers (sulfate of ammonia and superphosphate), plastics, detergents, dyes, drugs, explosives nitric acid,HNO3 used in the manufacture of fertilizers, explosives (TNT and dynamite) phosphoric acid,H3PO4 used as a food acid and in

Alkalis (water soluble bases): sodium hydroxide, NaOH caustic soda potassium hydroxide, KOH caustic potash aqueous ammonia, NH3(aq)

anti-rust products for cars Organic Acids: methanoic acid (formic acid), HCOOH found in ant stings ethanoic acid (acetic acid), CH3COOH found in vinegar butanoic acid (butyric acid), C3H7COOH the acid that gives rancid butter its characteristic smell

Properties

aqueous acidic solutions: sour taste turn blue litmus red electrical conductors corrode most metals react with carbonates and bicarbonates neutralise bases

aqueous solutions of bases (soluble bases are called alkalis): bitter taste change red litmus blue electrical conductors slippery feel neutralise acids

ArrheniusDefinitions an acid ionises in water (1884) to produce hydrogen ions, H+ (protons) only accounts for acids that: are aqueous solutions have hydrogen ions in their structure, eg, HCl

a base ionises in water to produce hydroxide ions, OH-

only accounts for bases that: are aqueous solutions (alkalis) have OH- already in their structures, eg, NaOH

does not account for amphotericsubstances does not account (those that can act as an acid or a for amphotericsubstances base) (those that can act as an acid or a base) Brnsted-Lowry Definitions an acid is a species that donates a a base is a species that accepts a proton(H+) proton (H+)

(1923)

an amphiprotic substance can act as a proton donor and as a proton acceptor hydrogen carbonate (bicarbonate) ion (HCO3-)is amphiprotic, it can either accept a proton to form carbonic acid (H2CO3) or it can donate a proton to form carbonate ion (CO32-) HB H+ + BB- + H+ HB

HB is acting as an acid by donating a proton, H+ B- is the conjugate base of the acid HB acid HCl HNO3 H2SO4 HSO4H2O conjugate base ClNO3HSO4SO42OH-

B- is acting as a base by accepting a proton, H+ HB is the conjugate acid of the base Bbase OHNH3 CO32HCO3H2O conjugate acid H2O NH4+ HCO3H2CO3 H3O+

efining & Using pH & pOH

neutral

Acid
pH

Base 4 5 6 7 8 9 10 11 12 13 14
pH

E x a m p l e s

1M HCl

coca Gastric cola, coffee, 0.1M juice, lemon wine tomaHCl ant juice, toes venom vinegar

tap water, saliva, cow's milk

pure soap, water, sea baking NaCl(aq), water, soda KNO3(aq)

detergents, toothpaste

0.1M deterhouse- NaOH, gents, 1M hold caustic washing NaOH cleaner oven soda cleaner

pOH

14

13

12

11

10

pOH

most acidic

<

----

-----

----

---------

least acidic

neutral

least basic

-----

--------

-----

-----

>

most basic

=14

pH
pH is a measure of the hydrogen ion concentration, [H+] pH is calculated using the following formula: pH = -log10[H+] Example 1: Find the pH of a 0.2mol L-1 (0.2M) solution of HCl Write the balanced equation for the dissociation of the acid HCl -----> H+(aq) + Cl-(aq) Use the equation to find the [H+]: 0.2 mol L- HCl produces 0.2 mol L1 H+ since HCl is a strong acid that fully dissociates Calculate pH: pH = -log10[H+] pH = -log10[0.2] = 0.7

pOH
pOH is a measure of the hydroxide ion concentration, [OH-] pOH is calculated using the following formula: pOH = -log10[OH-] Example 1: Find the pOH of a 0.1mol L(0.1M) solution of NaOH Write the balanced equation for the dissociation of the alkali NaOH -----> OH-(aq) + Na+(aq) Use the equation to find the [OH-]: 0.1 mol L-1 NaOH produces 0.1 mol L-1 OHsince NaOH is a strong alkali that fully dissociates Calculate pOH: pOH = -log10[OH-] pOH = -log10[0.1] = 1

Example 2: Find the pH of a 0.2 mol L-1 (0.2M) solution of H2SO4 Write the balanced equation for the dissociation of the acid H2SO4 -----> 2H+(aq) + SO42-(aq) Use the equation to find the [H+]: 0.2 mol L-1 H2SO4 produces 2 x 0.2 = 0.4 mol L-1 H+ since H2SO4 is a strong acid that fully dissociates Calculate pH: pH = -log10[H+] pH = -log10[0.4] = 0.4

Example 2: Find the pOH of a 0.1mol L-1 (0.1M) solution of Ba(OH)2 Write the balanced equation for the dissociation of the alkali: Ba(OH)2 -----> 2OH-(aq) + Ba2+(aq) Use the equation to find the [OH-]: 0.1mol L-1 Ba(OH)2 produces 2 x 0.1 = 0.2 mol L-1 OH- since Ba(OH)2 is a strong alkali that fully dissociates Calculate pOH: pOH = -log10[OH-] pOH = -log10[0.2] = 0.7

Hydrogen ion concentration, [H+], can be calculated using the following formula: [H+] = 10-pH

Hydroxide ion concentration, [OH-], can be calculated using the following formula: [OH-] = 10-pOH

Example: Find the [H+] of a nitric acid solution with a pH of 3.0 pH= 3.0 [H+] = 10-pH [H+] = 10-3.0 = 0.001mol L-1 You can check this answer by using the calculated value [H+] in the equation for pH to make sure you arrive at the original pH pH = -log10[H+] pH = -log10[0.001] = 3 We get the same value for pH using the calculated value for [H+], so the calculated value for [H+] is correct.

Example: Find the [OH-] of a sodium hydroxide solution with a pOH of 1 pOH = 1 [OH-] = 10-pOH [OH-] = 10-1 = 0.1 mol L-1 You can check this answer by using the calculated value [OH-] in the equation for pOH to make sure you arrive at the original pOH pOH = -log10[OH-] pOH = -log10[0.1] = 1 We get the same value for pOH using the calculated value for [OH-], so the calculated value for [OH-] is correct.

pH + pOH = 14
Example A(1): Find the pH of a solution of sodium hydroxide that has a pOH of 2 pH = 14 - pOH pH = 14 - 2 = 12 Example A(2): Find the [H+] in a solution of sodium hydroxide that has a pOH of 1 Calculate the pH pH = 14 - pOH pH = 14 - 1 = 13 Calculate [H+] [H+] = 10-pH [H+] = 10-13 = 10-13mol L-1 Example B(1): Find the pOH of a solution of hydrochloric acid that has a pH of 3.4 pOH = 14 - pH pOH = 14 - 3.4 = 10.6 Example B(2): Find the [OH-] of a sulfuric acid solution with a pH of 3 Calculate the pOH pOH = 14 - pH pOH = 14 - 3 = 11 Calculate [OH-] [OH-] = 10-pOH [OH-] = 10-11 = 10-11 mol L-1

Example A(3): Find the pH of 0.2mol L-1 sodium hydroxide Write the equation for the dissociation of NaOH: NaOH -----> Na+(aq) + OH-(aq) Use the equation to find [OH-]: 0.2mol L-1 NaOH produces 0.2mol L-1 OH-

Example B(3): Find the pOH of 0.2mol L-1 sulfuric acid Write the equation for the dissociation of H2SO4: H2SO4 -----> 2H+(aq) + SO42-(aq) Use the equation to find [H+]: 0.2 mol L-1 H2SO4 produces 2 x 0.2 = 0.4

since NaOH is a strong base that fully dissociates Calculate the pOH: pOH = -log10[OH-] pOH = -log10[0.2] = 0.7 Calculate pH: pH = 14 - pOH pH = 14 - 0.7 = 13.3

mol L-1 H+ since H2SO4 is a strong acid that fully dissociates Calculate the pH: pH = -log10[H+]: pH = -log10[0.4] = 0.4 Calculate pOH: pOH = 14 - pH pOH = 14 - 0.4 = 13.6

Acid-base Titration Calculations

Key Concepts acid-base reactions involve a proton transfer the acid donates a proton to the base acid-base reactions are also known as neutralisation reactions acid + base -----> salt + water acid A + base B -----> conjugate acid of base B + conjugate base of acid A (Lowry-Brnsted theory) H+ + OH- ------> H2O is the most general neutralisation reaction Equivalence point is the point at which the moles of H+ is equal to the moles of OHAn indicator is used to show the equivalence point during a titration A titration involves the progressive addition of one reactant from a burette (usually the acid), to a known volume of the other reactant in a conical flask (usually the base)

Calculations a. Write the balanced chemical equation for the reaction b. Extract all the relevant information from the question

c. Check that data for consistency, for example, concentrations are usually given in M or
mol L-1 but volumes are often given in mL. You will need to convert the mL to L for consistency. The easiest way to do this is to multiply the volume in mL x 10-3

d. Calculate the moles of reactant (n) for which you have both the volume(V) and concentration(M) : n = M x V e. From the balanced chemical equation find the mole ratio known reactant : unknown reactant

f.

Use the mole ratio to calculate the moles of the unknown reactant

g. From the volume(V) of unknown reactant and its previously calculated moles(n), calculate its concentration(M): M = n V Examples

1.

30 mL of 0.10M NaOH neutralised 25.0mL of hydrochloric acid. Determine the concentration of the acid a. Write the balanced chemical equation for the reaction NaOH(aq) + HCl(aq) -----> NaCl(aq) + H2O(l)

b. Extract the relevant information from the question:

NaOH NaOH V = 30mL , M = 0.10M V = 30 x 10-3L , M = 0.10M HCl V = 25.0mL, M = ? HCl V = 25.0 x 10-3L, M = ?

c. Check the data for consistency d. Calculate moles NaOH

n(NaOH) = M x V = 0.10 x 30 x 10-3 = 3 x 10-3 moles

e. From the balanced chemical equation find the mole ratio NaOH:HCl 1:1

f. Find moles HCl

NaOH: HCl is 1:1 So n(NaOH) = n(HCl) = 3 x 10-3 moles at the equivalence point

g. Calculate concentration of HCl: M = n V

n = 3 x 10-3 mol, V = 25.0 x 10-3L -3 M(HCl) = 3 x 10 25.0 x 10-3 = 0.12M or 0.12 mol L-1

2.

50mL of 0.2mol L-1 NaOH neutralised 20mL of sulfuric acid. Determine the concentration of the acid a. Write the balanced chemical equation for the reaction NaOH(aq) + H2SO4(aq) -----> Na2SO4(aq) + 2H2O(l)

b. Extract the relevant information from the question:

NaOH NaOH V = 50mL, M = 0.2M H2SO4

V = 20mL, M = ? V = 20 x 10-3L, M = ?

c. Check the data for consistency d. Calculate moles NaOH

V = 50 x 10-3L, M = 0.2M

H2SO4

n(NaOH) = M x V = 0.2 x 50 x 10-3 = 0.01 mol

e. From the balanced chemical equation find the mole ratio NaOH:H2SO4 2:1

f. Find moles H2SO4

NaOH: H2SO4 is 2:1

So n(H2SO4) = x n(NaOH) = x 0.01 = 5 x 10-3 moles H2SO4 at the equivalence point

g. Calculate concentration of H2SO4: M = n V

n = 5 x 10-3 mol, V = 20 x 10-3L -3 M(H2SO4) = 5 x 10 20 x 10-3 = 0.25M or 0.25 mol L-1

3.

25.0mL of 0.05M Ba(OH)2 neutralised 40.0mL of nitric acid. Determine the concentration of the acid. a. Write the balanced chemical equation for the reaction Ba(OH)2(aq) + 2HNO3(aq) -----> Ba(NO3)2(aq) + 2H2O(l)

b. Extract the relevant information from the question:

Ba(OH)2 Ba(OH)2 M=? V = 25.0mL, M = 0.05M V = 25.0 x 10-3L, M = 0.05M HNO3 HNO3 V = 40.0mL, M = ? V = 40.0 x 10-3L,

c. Check the data for consistency

d. Calculate moles Ba(OH)2

n = M x V = 0.05 x 25.0 x 10-3 = 1.25 x 10-3 mol Ba(OH)2 : HNO3 1:2

e. From the balanced chemical equation find the mole ratio

f. Find moles HNO3

Ba(OH)2 : HNO3 is 1 : 2 So n(HNO3) = 2 x n(Ba(OH)2) = 2 x 1.25 x 10-3 = 2.5 x 10-3 mol g. Calculate concentration of HNO3: M = n V n = 2.5 x 10-3moles, V = 40.0 x 10-3L M = 2.5 x 10-3 40.0 x 10-3 = 0.0625M or 0.0625 mol L-1

REDOX Reactions

REDOX Titrations
Key Concepts A REDOX titration is a volumetric method that relies on the oxidation of the analyte (substance to be analysed). The titrant (solution of known concentration) is often an oxidising agent. Common oxidising agents are:

a. permanganate ion (MnO4-)

MnO4-(aq) + 8H+ + 5e -----> Mn2+(aq) + 4H2O Eo = +1.51V purple permanganate ion (MnO4 ) is reduced to colourless manganese (II) ion (Mn2+)

b. dichromate ion (Cr2O72-)

Cr2O72-(aq) + 14H+ + 6e -----> 2Cr3+(aq) + 7H2O Eo = +1.23V 2orange dichromate ion (Cr2O7 ) is reduced to green chromium (III) ions (Cr3+) E(cell) = 0

At the equivalence point E(forward) = E(reverse), or,

If the REDOX reaction does not produce a well-defined colour change at the equivalence point, an indicator should be used in the titration. Starch can be used as an indicator for REDOX titrations using iodine as the titrant (iodine is a weak oxidising agent) because starch forms a blue complex with iodine. The REDOX titration curve is a plot of Electrode Potential (volts) vs volume of titrant or analyte.

Calculations

a. Write a balanced half equation for the oxidation reaction. b. Write a balanced half equation for the reduction reaction.
c. Add the oxidation and reduction half equations together to give a balanced REDOX reaction equation. d. Extract all the relevant information from the question.

e. Check the data for consistency, for example, concentrations are often given in M or mol
L-1 but volumes are often given in mL. You will need to convert the mL to L for consistency. The easiest way to do this is to multiply the volume in mL x 10-3.

f.

Calculate the moles of reactant (titrant) (n) for which you have both volume (V) and concentration (M): n = M x V

g. From the REDOX reaction equation find the mole ratio of known reactant (titrant) : unkown reactant (analyte) h. Calculate moles of unknown reactant (analyte) using this mole ratio. i. From the volume (V) of the unknown reactant (analyte) and its calculated moles (n), calculate its concentration(M): M = n V

Example A 0.0484M standard solution of potassium permanganate was titrated against 25.00mL of an iron (II) sulfate solution. The equivalence point, as indicated by a faint pink colour, was reached when 15.50mL of potassium permanganate solution had been added. Calculate the concentration of the iron (II) sulfate solution.

a. reduction half equation:

MnO4- + 8H+ + 5e -----> Mn2+ + 4H2O

b. oxidation half equation:

Fe2+ -----> Fe3+ + e

c. REDOX equation:
MnO4- + 8H+ + 5e 5Fe2+ MnO4- + 8H+ + 5Fe2+ -----> Mn2+ + 4H2O -----> 5Fe3+ + 5e -----> Mn2+ + 4H2O + 5Fe3+

d. Extract all the relevant information:

MnO4[MnO4-] = 0.0484 mol/L V (MnO4-) = 15.50 mL Fe2+ [Fe2+] = ? mol/L V (Fe2+) = 25.00 mL

e. Check the data for consistency: convert volumes in mL to L

MnO4[MnO4-] = 0.0484 mol/L V (MnO4-) = 15.50 x 10-3 L Fe2+ [Fe2+] = ? mol/L V (Fe2+) = 25.00 x 10-3 L

f. Calculate moles of known reactant (titrant):

MnO4[MnO4-] = 0.0484 mol/L V (MnO4-) = 15.50 x 10-3 L n (MnO4-) = M x V = 0.0484 x 15.50 x 10-3 = 7.502 x 10-4 mol

g. Find the mole ratio from balanced REDOX equation

MnO4- : Fe2+ 1:5

h. Calculate moles (n) of Fe2+

i.

n (Fe2+) = 5 x n (MnO4-) = 5 x 7.502 x 10-4 = 0.003751 mol

Calculate the concentration of Fe2+ [Fe2+] = n V = 0.003751 25.00 x 10-3 = 0.1500 mol/L Instrumental Techniques

Chromatography Techniques
Key Concepts

Chromatography is an analytical technique used to determine the purity of a substance or to separate a mixture into its components. The stationary phase refers to the solid or liquid to which components in a mixture bind or adsorb. The mobile phase refers to the liquid or gas that moves the components in a mixture over the stationary phase. Components in a mixture are separated based on their different abilities to bind or adsorb to the stationary phase, and on their different abilities to desorb or dissolve in the mobile phase.

In paper and thin layer chromatography the retardation factor, Rf, is a comparison of the distance travelled by a component to the distance travelled by the solvent. Comparison of Chromatography Techniques Type Paper Features inexpensive slow used for water soluble compounds a qualitative technique stationary phase:paper; mobile phase:pure solvent or solvent mixture Rf measured inexpensive faster than paper and more sensitive used for less polar compounds qualitative technique although components may be scraped off the plate & their masses measured stationary phase: plate coated with silica gel or Al2O3; mobile phase:pure solvent or solvent mixture Rf measured identification of biological sugars identifying components of pain-relieving preparations identifying components (eg, carboxylic acids) that might damage paper Uses identification of colours in inks or foods identification of amino acids separation of pigments in plant leaves

Thin Layer (TLC)

Gas (GC)

area under the peak measures the amount of the component present

expensive fast used for gases or easily vaporised compounds Mr < 300 both qualitative and quantitative technique stationary phase:either a sold (eg, glass beads) or liquid (eg, long chain hydrocarbon); mobile phase (carrier gas):helium, nitrogen, or some other inert gas Rf measured

analysis of air-borne pollutants analysis of athletes' urine samples for performance enhancing drugs analysis of oil spills analysis of essential oils in perfume preparation

Highperformance Liquid (HPLC)

area under the peak measures the amount of the component present

expensive but less expensive than GC fast but slower than GC used for organic compounds that decompose if vaporised or compounds with Mr > 300 both a qualitative and a quantitative technique stationary phase: small waxy solids; mobile phase (eluent): pure solvent or solvent mixture Rf measured

analysis of pharmaceuticals cyanide analysis analysis of organic pollutants in water analysis of toxic compounds in shell fish protein analysis

A Summary of Spectroscopy Techniques

Type Flame Tests Features inexpensive fast, but some colours may be masked by others making it unreliable qualitative technique limited application as many common metals (e.g., Al & Mg) do not colour a flame a type of emission spectroscopy which can be observed by the naked eye or by using a spectroscope to see a series of bright lines relatively inexpensive fast, requiring a set of standard solutions qualitative & quantitative a type of absorption spectroscopy limited to coloured solutions or compounds Uses Identification of metals in some salts Li+ Na+ K+ Ca2+ Sr2+ Ba2+ Cu2+ crimson yellow lilac brick red scarlet green green-blue

Colorimetry

copper (II) sulfate in garden sprays iron (III) concentration using KSCN to form the coloured Fe(CNS)2+complex coloured solutions such as food colourings wavelength of light is selected for maximum absorbance & a calibration curve is constructed of absorbance versus concentration

Atomic Absorption Spectroscopy (AAS)

expensive fast, requiring a set of standard solutions

mercury in shellfish lead in soil samples trace metals in mineral

quantitative a type of absorption spectroscopy that can be used for all metals and metalloids (semi-metals)

waters

correct hollow cathode tube selected & a calibration curve constructed of absorbance versus concentration. (solutions may have to be diluted)

UV-visible spectroscopy

expensive fast, requiring a set of standard solutions qualitative & quantitative a type of absorption spectroscopy limited to coloured solutions or compounds

concentration of some coloured pharmaceuticals in blood serum concentration of metal ions using coloured complexes concentration of food colourings wavelength of light selected for maximum absorbance and a calibration curve constructed of absorbance versus concentration

Infrared Spectroscopy
Key Concepts Infrared (ir) spectroscopy is used to identify particular bond types and functional groups in organic molecules by measuring a substance's absorption of infrared radiation at different frequencies. Wavenumber is the number of wavelengths per centimetre (cm-1). Organic groups show absorbance in the range ~1000 to 3000 cm-1. Infrared (ir) spectra show a 'fingerprint' region between ~1000 and 400 cm -1 which is

specific to a particular compound. The ir spectrum of an unknown compound can be compared to known spectra in order to identify the unknown compound. Infrared Spectrometer Atoms in molecules are continually vibrating. This vibrational energy is quantised. When molecules absorb infrared radiation they become hot and the atoms and molecules vibrate more vigorously. Molecules absorb infrared radiation at particular wavelengths depending upon which chemical bonds are present in the molecule. a. infrared radiation is produced by electrically heating a filament which is divided by mirrors into 2 beams, a reference beam and a sample beam. b. In the sampling area, a segmented rotating disk allows each beam to pass through alternately. c. The reference beam and the sample beam are combined into a beam of alternating segments. d. The detector measures the heat energy and the recorder records the results as a plot of percent absorption (or transmittance) as a function of wavenumber (cm-1) or wavelength (m). Infrared (ir) Spectra Particular chemical bonds absorb energy at a particular wavelength (wavenumber) regardless of the compound the bond is in. Some examples are given below: molecular vibration C-Cl C-C C-O wavenumber (cm-1) 700-800 750-1100 1000-1300 wavelength (m) 14.3-12.5 13.3-9.1 10-7.7

The Infrared (ir) Spectrometer

C=C C=O O-H (acids) C-H O-H (alcohols) N-H (primary amines) Examples of Infrared (ir) Spectra

1610-1680 1670-1750 2500-3300 2850-3300 3200-3550 3350-3500

6.2-6.0 6.0-5.7 4.0-3.0 3.5-3.0 3.1-2.8 3.0-2.9

The infrared (ir) spectrum of hexane, CH3CH2CH2CH2CH2CH3.

Bond types present C-H stretches (2850-3300 cm-1)

The infrared (ir) spectrum of 1-hexene, H2C=CHCH2CH2CH2CH3. Bond types present C-H stretches (2850-3300 cm-1) C=C stretches (1610-1680 cm-1) The infrared (ir) spectrum of ethanol, CH3CH2OH. Bond types present O-H (alcohol) stretches (3200-3550 cm-1) C-H stretches (2850-3300 cm-1) O || C H

The infrared (ir) spectrum of octanal,

CH3CH2CH2CH2CH2CH2CH2

Bond types present C-H stretches (2850-3300 cm-1) C=O stretches (1670-1750 cm-1) O || CH3CH2 C CH2CH3

The infrared (ir) spectrum of 2-pentanone,

Bond types present C-H stretches (2850-3300 cm-1) C=O stretches (1670-1750 cm-1)