Section 1 Atoms, Molecules & Stoichiometry Atomic Structure particle atomic symbol relative mass charge electron (e ) 0 e

paroton (p ) 1 or 1 p H
1 1

neutron (n)
1 0 n

position

1/1840 -1 unit (-1.6021 x 10 19 C ) outside the nucleus, moving very fast in shells (or more precisely orbitals, see Section 2) that occupy approximately the whole size of the atom

1 +1 unit (1.6021 x 10 19 C )

1 0

in the nucleus (of radius 10 15 m)

Atomic Mass Unit, Relative Isotopic Mass, RAM, RMM y y y y y Carbon-12 scale: the relative mass of a 12 C atom is defined to be 1200000
6 12 A C atom has a mass of 12 atomic mass units (a.m.u.) 6 1 atomic mass unit (a.m.u.) = 1/12 (mass of a 12 C atom) 6

The relative isotopic mass (or simply the isotopic mass) of an isotope is the mass of that isotope in the 12 C = 1200000 scale.
6

The relative atomic mass (or simply atomic mass) of an element is the weighted average of all the isotopic masses of all the natural occurring isotopes.

E.g. relative abundances of isotopes of oxygen: isotope relative isotopic mass relative abundance

O 15.995 99.76%

16

O 16.999 0.04%

17

O 17.999 0.20%

18

RAM = 15.995(0.9976) + 16.999(0.0004) + 17.999(0.002) = 16.00

relative formula mass of a compound (any compound) = sum of RAM of all elements in + formula unit of that compound relative molecular mass of a molecule (molecular substances only) = sum of RAM of all atoms present in the molecule

Mass Spectrometer Principle y Mass Spectrometer for y determining the mass-to-charge ratio (m/e) of a particle (cation of an element, e.g. C1 1 ) or molecular ion, e.g. CO , C1 ) if the charge is +1, the mass of the isotope or

+ 2

+ 2

molecule can be determined from the mass/charge ratio y y y the analysis of the sample (useful in organic chemistry) The sample is vaporized by (1) heating in the vaporization chamber (A) AND (2) under reduced pressure. The sample is bombarded by fast-moving e _ to form positively charged ions X + (ions of an element or molecular ions) in the ionization chamber (B) (usually +1 ions are formed). The pressure inside the mass spectrometer is very low to prevent ions from colliding with air molecules.

The +ve ions are accelerated by the electric field (C) The ions of different masses are deflected by the magnetic field (D) which is adjusted so that ions of a particular mass-to- charge ratio (m/e) are focused onto the ion detector (E) The ion detector responds to the mass-to-charge ratio (NOT mass!) of the ionized species From (1) the strength of the magnetic field, (2) the accelerating voltage & (3) the radius of the path, the (mass/charge) ratio of the particle can be calculated. If the charge of an electron (-1 unit) is known, the mass of the particle can be found.

y y

Mass spectrum: y-axis D peak height (or relative intensity) is directly proportional to the % abundance of the ionized species (e.g. x-axis D m/e ratio
14

N + or CO ),

+ 2

When the sample is not monoatomic, many peaks may arise:

Given: Mass spectrum of chlorine gas

(a) Explain why there are 5 peaks in the mass spectrum. (b) Relative atomic mass of chorine. (c) Ratio of relative abundance of C to D to E. D Solution: (a) Since there are 2 isotopes of C1, 3 types of chlorine molecular ions exist: 35 C1+ , 35 C1 37 C1+ , 37 C 37 C1+ Since C1 2 molecule can dissociate during the electron bombardment in the ionization chamber, atomic ions 35C1+ & 37 C1+ will also be detected. Total no. of peaks = 3+2 = 5 D Indicate the +ve charge on the ionized species!

35

C1 -

(b) RAM of C1 = (35)(3/4) + (37)(1/4) = 35.5 (a.m.u.) (c) Abundance of C 3/4 x 3/4 = 9/16 Abundance of D 2 x 1/4 x 3/4 = 6/16 Abundance of E 1/4 x 1/4 = 1/16 Ratio of relative abundance of C : D : E = 9 : 6 : 1 D Given: mass spectrum of a carbon- containing compound: Ion C+ 13 + C
12

Mass / a.m.u. 12.000 13.003

Relative intensity 100.00 1.12

D Find: relative atomic mass of C 12000 x100 + 13.003x1.12 D Solution: RAM = = 12.011 (NO unit!) (100 + 1.12) D Given: Elements X & Y form a compound with molecular formula XY 3 with the following mass spectrum:

D Find: (a) How is the molecular ion XY 3 + formed? (b) Relative atomic masses of X & Y = ? D Solution: (a) In the ionization chamber of the mass spectrometer, XY 3 molecules were bombarded by fast-moving electrons to give XY 3 + :

e 2c XY 3 (g) + t XY 3 + (g) + fast slow

(b) The peak at m/e ratio = 31 is due to X + ions. The peak at m/e ratio = 19 is due to Y + ions. RAM of x = 31, RAM of Y = 19 Mass Spectrum Composition of a Mixture z Application of Mass Spectroscopy in the analysis of the composition of a mixture: If a gas mixture containing 10% He, 30% Ne, 50% Ar & 10% Xe by volume is analyzed by mass spectroscopy, the following peaks of the molecular ion can be found (assuming each noble gas consists of 1 stable isotope only): m/e radio ion Relative intensity
D D D

4 He + 10

20 Ne + 30

40 Ar + 50

131 Xe + 10

Given: volume composition of air N 2 78%, O 2 21% & CO 2 1% (RAM: C= 12.0, N = 14.0, O = 16.0) Find: mass spectrum of air (molecular ions) Solution: volume composition = mole composition

Mole, P-V-T relationships of gases, Ideal Gas Law (Equation)

z z z z

z z

Boyles law: P-V relationship at constant T (absolute temp.!) D PV = constant for a fixed amount of gas Charles law: V-T relationship at constant P D V/T is constant for a fixed amount of gas P-T relationship at constant V D P/T = constant for a fixed amount of gas Avogadros law: equal volumes of gases at same conditions D equal no. of moles PV Ideal gas equation: = nR or PV = nRT T Relationship between density & molar mass (NOTE: the UNITS of mass must be consistent!)- The ideal gas equation can be rewritten for the calculation of the gas density ( , in g m 3 [or kg m 3 ]) For a gas of mass in (in g [or kg]) & a molar mass of M (in g mol 1 [or kg mol 1 ]), a volume of V (in m 3 ) at a pressure P (N m 2 , Pa): PV = nRT & = m/V

m ) RT P = ( ) RT M M PM RT DM= OR = P RT
D PV = ( D

Beware of the units: R = 8.31 J K 1 mol 1 ; For pressure: 1 Pa = 1 N m 2 [1 atm. = 101 kPa] For mass: 1 kg = 1000g For volume: 1 m 3 = 1000 dm 3 ; 1 dm 3 = 1000 cm 3 For density: 1 g dm 3 = 1 kg m 3 = 10 3 g cm 3

Daltons law of partial pressures

z

In a gas mixture, the partial pressure of each component gas is the pressure that the gas, would exert if it were the only gas occupying the total volume at that temperature. Daltons law can be derived from the ideal gas equation, i.e. RT RT P total = (n total ) = (n 1 + n 2 + n 3 +) V V RT RT RT + n2 + n3 + .. = n1 V V V
P total = P 1 + P 2 + P 3 + [P 1 = partial pressure of gas i]

The mole fraction (X i ) of a component in a mixture is defined as the no. of moles of that component over the total no. of moles of gases, i.e. Xi =
ni ntotal

PiV P V & n total = total , if the total pressure of the gas mixture is known, RT RT the partial pressure of component gas i is given by:

Since n i =

Xi =

ni P = i ntotal Ptotal

Pi -

ni P total - X i P total ntotal

D Given: Gaseous compound X contains mass % N (21.6), O (49.2), F (29.2), at 298 K & 1.01 x 10 5 N m 3 , density of X= 2.65 g dm 3 [RAM: N = 14.0: O = 16.0; F = 19.0] D Find: (a) empirical formula & (b) molecular formula of x D Solution: 21.6 49.2 29.2 : : = 1.543 : 3.075 : 1.537 (a) mole ratio N: O: F = 14 16 19 = 1 : 2 : 1 D empirical formula NO 2 F

(c) For an ideal gas, PV = nRT, M r =

RT

2.65 x10 3 molar mass of X = x 8.31 x 298 = 64.97 g mol 1 5 1.01x10 Let molecular formula of X be (NO 2 F) n (14.0+16.0x2+19.0)n = 64.97 n = 1, molecular formula: NO 2 F
D Given: aluminium chloride gas, T = 433 K, m 0.569g, V = 96.0 cm 3 , P = 80.0 kPa [RAM: Al=27.0, Cl = 35.5] D Find: [Assuming ideal gas law is valid] (a) apparent molar mass of aluminium chloride (b) apparent molecular formula of aluminium chloride (c) structure of aluminium chloride in the vapour D Solution: (a) PV = nRT m 0.569 M= RT = x 8.31 x 433 = 266.6 g mol 1 3 6 PV 80 x10 x96 x10

(b) empirical formula mass of AICI 3 = 27.0 + 3(35.5) = 133.5 molecular formula = (AICI 3 )n; n = 266.6/ 133.5 2 i.e. molecular formula AI 2 CI 6 exist as dinner (c)

D Given: At 500K & 70.0 kPa, 6.0 g of ethanoic acid vapour occupies a volume of 4.90 dm 3 [RAM: H=1.0, C 12.0: O = 16.0] D Find: [Assuming ideal gas law is valid] (a) apparent relative molecular mass of ethanoic acid (b) reason for the departure from expected RMM of CH 3 COOH D Given: 0.5 mole of H 2 and 0.5 mole of O 2 are introduced into a flask of constant Volume 10 dm 3 at 600C, after an electrical sparking, some water vapour is formed. D Find: (a) composition of the mixture in terms of mole fractions (b) partial pressure of each gas in mixture

D Given: In a flask of constant volume, the pressure of a mixture of gases X & Y at 200C is 4.5 atm. At -40C, X is condensed & the pressure becomes 1.5 atm. D Find: mole fraction of X in the mixture D Given: Gas containers A and B each contains an ideal gas at low pressure & 25C. Volume of container A = 2 x volume of container B, but the no. of moles of ideal gas contained in A is only half of that in B

D Given: hydrocarbon X, density of 1.15 g dm 3 at 95.3 kPa pressure & 298 K (1 kPa = 1 x 10 3 N m 2 ) D Find: molar mass & molecular formula of X D Give: At 100 kPa, a certain temperature & the presence of a catalyst, a certain volume of C 2 H 6 (g) is cracked into C 2 H 4 (g) & H 2 (g). The volume of the gas increases by 30% after cracking. D Find: (Under the same conditions) (a) Mole fractions of C 2 H 6 (g), C 2 H 4 (g) & H 2 (g) respectively (b) Partial pressures of C 2 H 6 (g), C 2 H 4 (g) & H 2 (g) respectively

Stoichiometry, Limiting Reagents & Yield

z

Stoichiometry is the numerical relationship between the amounts of reactants & products in a chemical reaction.

The exact amounts of reactants as given by the balanced equation are called the stoichiometric amounts. The yield is the amount of product formed. The theoretical yield is the amount of product formed as predicted from the stoichiometric of the reactants if the reaction goes completely. The actual yield is the actual amount of product obtained.

z z

z z

percentage yield =

x 100%

If the % yield is 100%, the reaction is said to be quantitative, or produces a quantitative yield, If the % yield is less than 100%, the reaction is said to be non-stoichiometric. A low yield may be caused by z the presence of reversible reaction(s), z impure reactants, z side reactions &/or z the loss of products during purification. If the reactants are not in stoichiometric amounts, the one that is NOT in excess is called the limiting reactant (or reagent), the one that is in excess is called the excess reactant (or reagent).
Note that the theoretical yield is calculated from the amount of the limiting reactant.

D Given: 15.00 g 4-nitrobenzoic, acid (O 2 N-COOH) reacted with excess PCl 5 to give 13.60 g of 4-nitrobenzoyl chloride (O 2 N-COCl) [RAM: H=1.0, C= 12.0, N- 14.0, O-16.0, Cl= 35.5] D Find: % yield of the reaction D Given 20.0 g of (CH 3 ) 3 COH reacted with 35.0 g of HCl to give 18.0 g of (CH 3 ) 3 CCl D Find: (a) the limiting reactant (b) percentage yield of (CH 3 ) 3 CCl Calculation involving Equations D Given: 5200 g of a hydrated sodium carbonate (Na 2 CO 3 xH 2 O) were dissolved in water. Excess CaCl 2 (aq) is added to the resulting solution to give 4.20 g of a precipitate. [RAM: H=1.0, C=12.0, O=16.0 Na=23.0, Ca=40.1] D Find:

(a) formula of the hydrated sodium carbonate (b) give the assumption

D Given: An air bag in car contains 130 g of sodium azide N a N 3 When a car crash occurs, the crash sensor in car sends an electric signal to an ignitor to heat up the sodium azide. Within 0.03 sec, the sodium azide decomposes to give sodium metal & nitrogen gas, which inflates the cars air bags. [RAM: N=14.0; Na=23.0] D Find: (a) maximum volume of the N 2 formed at 298K & 101 kPa (b) hazard of sodium vapour formed

Formula, Chemical Equations, Calculation & Titration

z

A primary standard is a substance that can be used to prepare a standard solution without standardization (i.e. by dissolving a known mass of that substance in a solvent to give a known volume of the solution, the morality of that solution can be calculated) z Usually solid z Must be very pure / with constant composition, does not absorb moisture nor lose water easily, stable in air, soluble in water & with high relative formula mass Examples of primary standards: z (COOH) 2 2H 2 O(s) [acid] z constant boiling hydrochloric acid [acid] (NOT HNO 3 ) z aminosulphonic acid (sulphamic acid) NH 2 SO 3 H [acid] z anhydrous Na 2 CO 3 (s) [base] z K 2 Cr 2 O 7 (s) [OA] z KIO 3 (s), KBrO 3 (s) [OA] z Na 2 C 2 O 4 (s) [RA] z Fe(NH 4 ) 2 (SO 4 ) 2 6H 2 O ammonium iron(II) sulphate(VI)-6-water [RA] z Fe(s) wire [RA]

The following are NOT primary standards: z NaOH(s): absorbs moisture in air z l 2 (s), Br 2 (1): volatile, reacts with RA (SO 2 /H 2 S) in air cannot be prepared in highly pure form solid z AgNO 3 (s): decomposes by light z Na 2 S 2 O 3 (s): decomposes by acids, bases, OA, microorganism z Standardization involving redox reagents: primary standards 2 5C 2 O (aq) * + 2MnO (aq) + 16H + (aq) t 2Mn 2+ (aq) +8H 2 O(1)+10CO 2 (g) 4 4 2 2 3C 2 O (aq) * + Cr 2 O (aq) * + 14H + (aq) t 2Cr 3+ (aq) + 7H 2 O(1) + 6CO 2 (g) 7 4 5Fe 2+ (aq) * + MnO (aq) + 8H + (aq) t 5Fe 3+ (aq) + Mn 2+ (aq) + 4H 2 O(1) 4 5H 2 O 2 (aq) + 2MnO (aq) + 6H + (aq) t 2Mn 2+ (aq) + 5O 2 (g) + 8H 2 O(1) 4 2+ z Fe (aq) is easily oxidized by air in alkaline / neutral medium, must be used in acidic medium [dilute H 2 SO 4 (aq) must be used] z KMnO 4 is acidified with dilute H 2 SO 4 (aq), NOT HNO 3 [OA], nor HCl(aq) [ Cl will be oxidized to give C1 2 ], K 2 Cr 2 O 7 can also be acidified will dilute 2 HCl(aq) [Cl cannot be oxidized by Cr 2 O ] 7
z

Preparation of standard I 2 (aq) I 2 (aq) + I (aq) t I 3 (aq) IO (aq) + 5I (aq) + 6H + (aq) t 3I 2 (aq) + 3H 2 O(1) 3 z Since iodine is volatile, we cannot prepare standard solution of iodine directly by accurately weighing a certain amount of I 2 (s) & dissolving the I 2 (s) in water.
z

The standard I 2 solution is prepared (& usually used immediately) by the addition of a known amount of potassium iodate(V) KIO 3 into excess I in an
acidic medium (must be dilute H 2 SO 4 , NOT conc. H 2 SO 4 , NOT HNO 3 , NOT HCI) I 2 (aq) is unstable in alkaline medium [disproportionates to I = (aq) & IO (aq)], I 2 must be used in acidic medium. 3 Standard Br 2 (aq) can be similarly prepared from KBrO 3 & excess Br = (aq)

in acidic medium (dilute H 2 SO 4 ) Titration of iodine (in flask) against thiosulphate (in burette) z Standard I 2 (in conical flask) can be used to standardize Na 2 S 2 O 3 (in burette) using starch indicator (in flask). 2 2 (aq) t S 4 O (aq) + 2I (aq) I 2 (aq) + 2S 2 O 3 6 Starch + I 2 (aq) <=> blue complex z Since starch irreversibly combines with iodine at a high concentration of I 2 (aq) (so that the I 2 will not be released from starch at the equivalence point), starch solution should be added at the later stage of the titration (when the solution has just turned from brown to pale yellow). After the addition of starch, the mixture turns deep blue. z The end point is indicated by the complete disappearance of the blue colour of the starch-iodine complex

Back Titration

Back titration: ammonium salt The amount of NH 4 NO 3 (or other ammonium salt) in a sample is determined by the addition of an excess known volume of standard alkali, e.g. 50.0 cm 3 of 1.00M KOH. The reaction mixture is then warmed to drive off the NH 3 formed. After the reaction has completed (no alkaline gas evolved), the excess KOH can be determined by titration with standard acid, e.g. 1.00 M HCI.

NH 4 NO 3 (aq) + KOH(aq) t KNO 3 (aq) + NH 3 (g) + H 2 O(1) KOH(aq) + HCI(aq) t KCI(aq) + H 2 O(1) no of moles of KOH = no. of moles of NH 4 NO 3 + no. of moles of HCI