Chapter 1: Matter

1.0

MATTER Anything that occupies space and possesses mass is called matter. Example: air, earth, animals, trees, atoms, The three states of matter are solid, liquid and gas
Matter

Separation by physical method

Mixtures

Pure Substances

Heterogeneous Mixtures

Homogeneous Mixtures

Compounds

Figure 1.1.1: Classification of matter 1.1 Atoms and Molecules

Separation by chemical method

Elements

1.1.1 Atom In an atom, there are three subatomic particles: proton (p), neutron (n) and electron (e). The number of protons = the number of electrons The protons and neutrons of an atom are packed in an extremely small nucleus. Therefore, nucleus contains most of the atoms mass. The relative mass of an atom is almost the same as its nucleon number (p + n). The nucleon number is sometimes used as the electron nucleus approximate relative mass in calculations. cloud The number of proton it contains determines the positive charge of the nucleus. The electrons move rapidly around the nucleus of an atom, and the space they occupy as they move defines the volume of the atom electrons cloud. Particle p n e Charge +1 0 -1 Relative Mass 1.0 amu 1.0 amu 0.0

1.1.2 Atomic (Nuclide) Symbol or Notation for Nuclides X = element symbol charge A = Nucleon Number of the nuclide X =Z+n

A Z

Z = Proton Number of the nuclide X =p

Chapter 1: Matter

Example 1.1.1:

202 80

Hg 2

2+

the right superscript shows that the total charge on the ion is 2+ the right subscript shows that the ion is formed from two mercury atoms. the left superscript: nucleon number of mercury, A = 202 the left subscript: proton number of mercury, Z = 80 the number of neutrons in a nucleus of mercury = 202 80 = 122 Example 1.1.2: Give the number of protons, neutrons and electrons in each of the following species: (a)
200 80

Hg (b)

63 29

Cu

(c)

17 8

O 2 (d)

59 27

Co 3+

Number of Symbol
200 80 63 29 17 8

proton 80 29 8 27

neutron 120 34 9 32

electron 80 29 10 24

Charge

Hg Cu

0 0 -2 +3

O 2 Co 3+

59 27

Example 1.1.3: Write the appropriate notation for each of the following nuclide: Number of proton 2 1 1 7 neutron 2 2 1 7 electron 2 0 1 10
1 4 7

Species A B C D

Notation for nuclides

4 2 3 1

B+ C

2 1

D 3

Exercise 1.1.1:
1)

Atom

3 9 1 9

K consists of ___ neutrons and ___ electrons.

Ans: (20, 19)

2)
3) 4)

An element Y contains 22 neutrons and 18 electrons. What is the proton number and nucleon number of the element? Write the symbol of Y. Ans: (18, 40) An ion X2 has 34 neutrons and 30 protons. Determine the nucleon number and the number of electrons in the ion. Ans: (64, 32) Determine the number of electrons and neutrons in the following species: 55 n 2 + , 19 F 23 M 9

Chapter 1: Matter

Ans: Mn2+ : (21,32) Note:

F- : (10,10)

1) The proton number, Z, is the nuclear charge and also the number of electrons in a neutral atom of the element. 2) no. p = no. e atom (neutral) 3) no. p > no. e positively charged cation (atom lost electrons) 4) no. p < no. e negatively charged anion (atom gained electrons) 1.1.3 Isotope Isotopes are termed as two or more atoms of the same element that have the same number of protons in their nucleus but different number of neutrons. Protium Isotopes of hydrogen Proton number Number of neutrons
1 1

Deuterium
2 1

Tritium
3 1

H
1 0

H
1 1

H
1 2

Uranium-235 Isotopes of uranium Proton number Number of neutrons

235 92

Uranium-238
238 92

U
92 143

U
92 146

Example 1.1.4 : For the following nuclides: 1 3 1 4 1 5 6T , 6 R and 7 Z a) write the nuclides that are isotopes. 1 3 1 4 6T and 6 R (reason: same proton number but different nucleon number) b) state the atoms that have the same number of neutrons. 1 4 1 5 6 R (no. neutrons = 14 6 = 8) and 7 Z (no. neutrons =15 7 = 8) Notes: Isotopes of an element have the same, (a) number of protons (proton number) (b) charge of nucleus of the atoms (ionization energy; electron affinity; size of the atom; electronegativity are the same) (c) number of electrons in a neutral atom (d) electronic configuration (the number of valence electrons) (e) chemical properties Isotopes of an element have different, (a) number of neutrons (nucleon number) in the nucleus of the atoms (b) relative isotopic mass

Chapter 1: Matter

(c)

physical properties (e.g boiling point / melting point, density, effusion rate,)

1.1.4 Molecule A molecule consists of a small number of atoms joined together by covalent bond. Diatomic molecule: contains two atoms (example: H2, Cl2, HCl, CO,) Polyatomic molecule: contains more than two atoms (example: H2O, NH3) 1.1.5 Ion An ion is a charged species formed from a neutral atom or molecule when electrons are gained or lost as the result of a chemical reaction. Cation: a positively charged ion (number e < number p) (example: Mg2+, NH + ) 4 Anion: a negatively charged ion (number e > number p) (example: Cl , OH ) Monatomic ion: ion contains only one nucleus (example: Fe3+, S2 ) Polyatomic ion: ion contains more than one nucleus (example: H3O+, CN ) 1.1.6 Relative Mass
(a) Relative Atomic Mass, Ar of an element

Ar =

average assof oneatomof theelem ent m 12 1 of 12 x m ass oneatomof C

The average relative isotopic mass of the atoms must be used for calculation because most elements consist of a mixture of isotopes.
(b) Relative Molecular Mass, Mr of a molecular substance

Mr =

average assof onem olecule thesubstance m of 12 1 of 1 2 x m ass oneatomof C

formula.

or

= sum of the relative atomic masses of all the atoms shown in the molecular

Example 1.1.5:

= 2 (Ar of H) + Ar of O = 2(1.008) + 15.999 = 18.15 relative molecular mass of CaCl2 = 40 + 2(35.5) = 111 relative molecular mass of SO42 = 32 + 4(16) = 96

Mr of H2O

Notes: Ar and Mr dimensionless Molecular mass, atomic mass atomic mass unit (amu)

Exercise 1.1.2

Chapter 1: Matter

1) 2) 3)

Determine the relative atomic mass of an element X if the ratio of the atomic mass of X to carbon-12 atom is 0.75. Ans: (9.0) Relative atomic mass of chlorine atom is 35.5. Explain why this value is not a whole number. Relative atomic mass of bromine atom is 80. What is the mass of bromine atom compared to carbon-12 atom? Ans: (6.67) Calculate the relative molecular mass of C5H5N. Ans: (79)

4) 1.1.7

Mass Spectrometer Mass spectrometer is used to determine: i) Relative atomic mass of an element ii) Relative molecular mass of a compound iii) Types of isotopes that are found in the naturally occurring element including the abundance of the isotopes and its relative isotopic mass. iv) Recognize the structure of the compound in an unknown sample. A pump maintains a vacuum inside the mass spectrometer as any air molecules inside would block the movement of the ions and to avoid the contamination of the sample. There are five main stages:
Vaporisation chamber Acceleration chamber (Electric field)

Magnetic field

A Vacuum
Ionization chamber
35

B
+

37

Cl

Cl

Ion detector Figure 1.1.2: Mass Spectrometer

(a) (b)

Vaporisation Chamber Sample of the element is vaporised into gaseous atom Ionisation Chamber A gaseous sample (atom or molecule) is bombarded by a stream of high-energy electrons that are emitted from a hot filament. Collisions between the electrons and the gaseous atom (or molecule) produce positive ions by dislodging an electron from each atom or molecule. M samle p M + e

f l mn ia e t

M+ samle p

+ e

s ml a pe

+e

f l mn ia e t

M+

(c)

Acceleration Chamber (Electric field)

Chapter 1: Matter

The positive ions are accelerated by an electric field towards the two oppositely charged plates. The electric field is produced by a high voltage between the two plates. The emerging ions are of high and constant velocity. (d) Magnetic field The positive ions are separated and deflected into a circular path by a magnet according to its mass/charge (m/e) ratio. Positive ions with small m/e ratio are deflected most and appear near A. Ions with large m/e ratio are deflected least and appear near B (Figure 1.1.2). (e) Ion detector The numbers of ions and types of isotopes are recorded as a mass spectrum. In practice, the ion detector is kept in a fixed position. The magnetic field is varied so that the positive ions of different masses arrive at the detector at different times. Mass spectrum: the horizontal axis shows the m/e ratio or nucleon number or isotopic mass or relative atomic mass of the ions entering the detector. The vertical axis shows the abundance or detector current or relative abundance or ion intensity or percentage abundance of the ions. The height is proportional to the amount of each isotope present. Information from a mass spectrum of an element i) the isotopes which are present in the element ii) the relative isotopic mass of each isotope iii) the abundance of each isotope Thus, the relative atomic mass of the element can be determined Example 1.1.6 : Relative abundance Mass Spectrum of Magnesium 63

8.1

9.1

24

25

26

m/e

The mass spectrum of magnesium shows that naturally occurring magnesium consists of three isotopes: 24Mg, 25Mg and 26Mg. The height of each line is proportional to the abundance of each isotope. In this example, 24 Mg is the most abundance of the three isotopes.

Ar of Mg

(24 a.m.u. x 63) + (25 a.m.u. x 8.1) + (26 a.m.u x 9.1) (63 + 8.1 + 9.1) = 24.33

Chapter 1: Matter

Ar =

Q m Q
i i i i

where Q = the abundance of an isotope of the element = the percentage of the isotope found in the naturally occurring element m = the relative isotopic mass of the element Notes : 1) The height of each peak measures the relative abundance of the ion which gives rise to that peak. 2) The total number of peaks in the mass spectrum of an element shows the types of naturally occurring isotopes. 3) The ratio of mass/charge for each species is found from the value of the accelerating voltage associated with a particular peak. Many ions have a charge of +1 elementary charge unit, and the ratio m/e is numerically equal to m, the mass of the ion. (1 elementary charge unit = 1.60x10 19 C) 4) The ion with the highest value of m/e is the molecular ion, and its mass gives the molecular mass of the compound Exercise 1.1.3 1. Fig 1.3 shows the mass spectrum of the element rubidium, Rb. a) What isotopes are present in Rb? b) What is the percentage abundance of each isotope? c) Calculate the relative atomic mass of Rb. Abundance 18

2.

7 The mass spectrum of neon, Ne consists of three lines corresponding to m/e ratio of 20, 21 and 22 with relative 85 87 intensities of 0.910, 0.0026 and 0.088, respectively. m Fig 1.3 a) Explain the significance of these data e [The mass/charge ratios refer to the singly-charged ions 20 21 22 from the isotopes present in the sample: 10 Ne, 10 Ne, 10 Ne the relative intensities show the relative abundance of each isotope in the sample.] b) Calculate the relative atomic mass of Ne. Ans: (20.2) c) Sketch the mass spectrum that would be obtained from naturally occurring Ne.

3.

6 7 The atomic masses of 3 Li and 3 Li are 6.0151 amu and 7.0160 amu respectively. What is the relative abundance of each isotope if the relative atomic mass of lithium is 6.941 amu? Ans:(92.51%)

4.

Naturally occurring iridium, Ir is composed of 2 isotopes 191 Ir and 193 Ir in the ratio of 5:8. The relative isotopic mass of 191 Ir and 193 Ir are 191.021 and 193.025 respectively. Calculate the relative atomic mass of iridium. Ans:(192.254)

Chapter 1: Matter

5.

Determine the relative atomic mass of copper from the mass spectrum shown below.

relative abundance

7 3 m/e 63 6. 65 Ans: (63.6)

The ratio of relative abundance of naturally occurring of chlorine isotopes is as follow:

35 37

Based on the carbon-12 scale, the relative atomic mass of 35Cl=34.9689 and 37Cl=36.9659. Calculate the Ar of chlorine. Ans:(35.45) 7. A sample of carbon dioxide gas that composes of isotopes 12C, 13C, 16O and 18O is analysed using the mass spectrometer. How many peaks will be observed in the mass spectrum? Ans: (6) 1.1.4 Chemical Formula

Cl = 3.127 Cl

Empirical Formula indicates which elements are present and the simplest whole-number ratio of their atoms in a molecule. Molecular Formula shows the exact number of atoms of each element in the smallest unit of a substance.
molecular formula = (empirical formula)n

Molecules Water Hydrogen peroxide Benzene Etyne

Empirical formula H 2O HO CH CH

Molecular Formula H 2O H2O2 C6H6 C2H2

n 1 2 6 2

Chapter 1: Matter

Note: The empirical formula and the molecular formula of a compound could be the same (NH3, CO2). Two molecules might have different molecular formulae but the same empirical formula.

A.

Calculating the empirical formula from the masses of constituents

Example: 18.3 g sample of hydrated compound contained 4.0 g of calcium, 7.1 g of chlorine and 7.2 g of water only. Calculate its empirical formula. Solution: Constituent Mass/g Amount/mol Simplest ratio of relative amount Empirical formula = CaCl2.4H2O Exercise 1.1.4: 1) 2)
3)

Ca 4.0 4.0 = 0.10 40 .0 0.10 = 1.0 0.10 1

Cl 7.1 7.1 = 0.20 35 .5 0.20 = 2.0 0.10 2

H2O 7.2 7.2 = 0.40 1 8 0.40 = 4.0 0.10 4

A sample of a hydrated compound was analyzed and found to contain 2.10 g of cobalt, 1.14 g of sulphur, 2.28 g of oxygen and 4.50 g of water. Calculate its empirical formula. 10.00 g sample of a compound contains 3.91 g of carbon; 0.87 g of hydrogen and the remainder is oxygen. Calculate the empirical formula of the compound. 10.00 g of hydrated barium chloride is heated until all the water is driven off. The mass of anhydrous compound is 8.53 g. Determine the value of x in BaCl2.xH2O. n=
molar mass ; empirical formula mass

molecular formula = (empirical formula)n

Example:

Ascorbic acid (vitamin C) cures scurvy and may help prevent the common cold. It is composed of 40.92% carbon, 4.58% hydrogen and 54.50% oxygen by mass. The molar B. Calculating the empirical formula from percentage composition by mass mass of ascorbic acid is 176 g mol 1. Determine its empirical formula and molecular mass. Solution: C H O Element Mass/g 40.92 4.58 54.50 40 .92 54 .50 Amount/mol = 3.41 4.58 = 3.41 12 16 3.41 4.58 3.41 =1 = 1.33 =1 3.41 3.41 3.41 Simplest ratio 1x3 1.33x3 1x3 3 4 3 Empirical formula = C3H4O3
molar mass n= empirical formula mass

Molecular formula

= (C3H4O3)n = (C3H4O3)2

176 =2 88

10

= C6H8O6

Chapter 1: Matter

Note: You must never round off values close to whole number in order to get a simple ratio, but multiply the value by a factor until we get a whole number. However, if the value is very close to whole number ( 0.01), it is allowed to round off the value. Exercise 1.1.5 1) Allicin is the compound responsible for the characteristic smell of garlic. An analysis of the compound gives the following percent composition by mass: C: 44.4%; H: 6.21%; S: 39.5%; O: 9.86%. Calculate its empirical formula. What is its molecular formula given that its molar mass is about 162 g mol 1. Determine the formula of a mineral with the following mass composition: Na=12.1%, Al=14.2%, Si=22.1%, O=42.1%, H2O=9.48%. Calculating the empirical formula from elemental analysis data Example: Solution: 1.00 g sample of compound A was burnt in excess oxygen producing 2.52 g of CO 2 and 0.443 g of H2O. Determine the empirical formula of the compound. In 1 mol of CO2 there is 1 mol of C In 1 mol of H2O there are 2 moles of H atoms
m
C

2)

= 2.52 g CO

12.0 g C 44.0 g CO

= 0.688 g C
2

=0.443 g H O x
2

2g H 18.0 g H O = 0.0492 g H
2

the mass of oxygen

= mass of sample (mass of C + mass of H) = 1.00 g (0.688 g + 0.0492 g) = 0.263 g O C 0.688 0.688 = 0.0573 12 .0 H 0.0492 0.0492 = 0.0492 1.00 0.0492 = 3.00 0.0164 3.00x2 6 O 0.263 0.263 = 16 .0 0.0164 0.0164 = 1.00 0.0164 1.00x2 2

Element Mass/g Amount/mol

0.0573 = 3.49 0.0164 Simplest ratio of relative amount 3.49x2 7 Empirical formula = C7H6O2 Exercise 1.1.6:

11

Chapter 1: Matter

1)

The combustion of 0.146 g of compound B gave 0.374 g of carbon dioxide and 0.154 g of water. Assuming that B contains carbon, hydrogen and oxygen only, determine its empirical formula. An organic compound, X which contains only carbon, hydrogen and oxygen, has a molar mass of about 85 g mol 1. When 0.43 g of X is burnt in excess oxygen, 1.10 g of carbon dioxide and 0.45 g of water are formed. a) What is the empirical formula of X? b) What is the molecular formula of X? A compound Y with chemical formula as shown below: CH2=CHCOOCH3 a) Write the empirical formula and molecular formula of the compound. b) Calculate the percentage composition of carbon in the compound X. Ans:(55.8%)

2)

3)

1.2 Mole Concept Mole: The amount of substance that contains as many elementary (atoms/molecules/ions) as there are atoms in exactly 12.000 g of carbon-12. particles

One mole of carbon-12 atoms has a mass of exactly 12.000 grams and contains 6.023x1023 atoms. 1 mole of atoms of an element = the relative atomic mass of the element in grams = Ar grams = 6.023x1023 elementary particles/entities

n (mole)=

mass, m molar m ass, M

Molar Mass: The mass (in grams) of 1 mole of units (atoms/molecules/electrons/ions) of a substance. Avogadro Constant (symbol: L @ NA) NA = 6.023x1023 mol 1 elementary particles/entities/units Example 1.2.1: 1.0 mol of chlorine atoms 1.0 mol of chlorine molecules 1.0 mol of calcium bromide = 6.023x1023 chlorine atoms = 35.5 g Cl = 6.023x1023 chlorine molecules= 2(35.5) g = 71.0 g Cl2 = 6.023x1023 x 2 chlorine atoms = 6.023x1023 units of CaBr2 = 200 g CaBr2 23 = 6.023x10 calcium ions = 6.023x1023 x 2 bromide ions

1.0 mol of ammonia, NH3 contains 1.0 mol of nitrogen atoms and 3.0 mol of hydrogen atoms. 1.0 mol of phosphorus, P4 contains 4.0 mol of phosphorus atoms. 1.0 mol of Na2SO4.10H2O contains 2.0 mol of natrium ions, 1.0 mol of sulphur atoms, 4.0 mol of oxygen atoms and 10.0 mol of water molecules.

12

Chapter 1: Matter

Relationship between mole, mass, Ar @ Mr and amount of particles In general, if the relative molecular mass of SO2 = 32 + 2(16) = 64 the weight of SO2 = 64 a.m.u. the mass of 1.0 mol of SO2 = 64 g the mass of 6.023x1023 SO2 molecules = 64 g the mass of one SO2 molecule = ________ g the molar mass of SO2 = 64 g/mol Notes :
The amount of A (mol) = = Mass A (g) Molar mass A (g/mol) Number of particles A NA

1.0 mol substance

= 6.023x1023 elementary entities/units/particles (atoms/ions/molecules/electrons) = Ar @ Mr grams = 22.4 litres at STP (i.e.: P= 1 atm & T= 273.15K)(molar volume of gas) = 24.0 dm3 at room temperature

Example 1.2.2: Calculate the number of atoms in 0.20 mol of magnesium. The number of Mg atoms
ol g = 0.20 m M x 6.023 x 10 23 atom s 1.0 m M ol g

= 1.2 x 1023 atoms. Example 1.2.3: Calculate the mass of (NH4)2CO3 that contains a) 0.300 mol NH4+ b) 6.023 x 1023 hydrogen atoms (a) The mass of (NH4)2CO3 = 0.300 mol NH4+ x
96 g (NH ) CO
4 2 3

2.0 m NH ol

+ 4

= 14.4 g

(b)

The mass of (NH4)2CO3 = 6.023x1023 H atoms x = 12.0 g

96 g (NH 4 ) 2 CO 3 8 x 6.023 x 10 23 H atoms

Exercise 1.2.1:
1) 2) 3)

How many atoms are there in 17 g of NH3 gas? Calculate the amount of oxygen atoms in 80 g of CuSO4. What is the mass of one HCl molecule?

Ans:(1.8x1024) Ans:(2 moles) Ans:(6.06x10 23)

13

Chapter 1: Matter 4) 5) 6)

How many moles of Fe2O3 are there in 1.00 kg of rust? What is the number of atoms in 2.5 g of phosphorus, P4?

Ans:(6.3) Ans:(4.85x1022)

What mass of sulphur dioxide, SO2 contains the same number of molecules as are in 1.00 g of ammonia? Ans:(3.77 g)

1.2.1 Mole Concept of Gases Molar volume of any gas at STP, V m = 22.4 dm 3 mol STP = standard temperature and pressure Where T = 273.15 K P = 1 atm @ 760 mmHg
Amount of gas at STP, n =
1

V, Volume of gas (L) Vm (22.4 dm3 mol 1)

Example 1.2.4: How many moles are there in 6.5 L oxygen at STP?
n

= 6.5 L O2 x

1 mol O 22.4 L

= 0.29 mol

Note: Do not use 22.4 L as the molar volume at temperatures and pressures other than 273 K and 1 atm.

Exercise 1.2.2: 1) 2) 3) A balloon is filled with hydrogen gas at STP. If the volume of the balloon is 2.24 dm3, calculate the amount of hydrogen gas. Ans:(0.1 mol) Calculate the volume of 24x1023 molecules of gas at STP. A sample of carbon dioxide has a volume of 56 cm3 at STP. Calculate (a) the number of moles of gas molecules, (b) the number of molecules, and (c) the number of oxygen atoms in the sample. Ans:(89.6 L) Ans:(0.0025) Ans:(1.5x1021) Ans:(3.0x1021)

1.2.2 Concentration Units The concentration of solutions is the quantity of dissolved substance per unit quantity of solvent in a solution. Concentration is measured in various ways: concentration (formerly molarity), weight percent, weight/volume percent, molal concentration (or molality), mass concentration, mole fraction, or parts per million (ppm). (a) Molarity, M The number of mole of solute dissolved per unit volume. (unit: mol L 1 @ mol dm 3 @ M)
1L Molarity, M = no. mole solute no. L solution 14 1mL 1 dm3 = = = 1 dm3 1 cm3 1000 cm3

Chapter 1: Matter

Example 1.2.5: A matriculation student prepared a solution by dissolving 0.586 g of sodium carbonate, Na2CO3 in 250.0 cm3 of water. Calculate its molarity. M (Na2CO3(aq)) = L 1. Exercise 1.2.3: 1) 2) What is the molarity of 85.0 mL ethanol solution that contains 1.77 g of ethanol, C2H5OH? [Ar C = 12.0, H = 1.0, O = 16.0] Ans:(0.453) Calculate the molarity of a solution of 1.71 g sucrose (C12H22O11) dissolved in litre of water.[Ar H = 1.0, C = 12.0, O = 16.0] Ans: (0.0100) How many grams of potassium dichromate, K2Cr2O7 required to prepare a solution of 250 mL with 2.16 M? Ans:(159) Calculate the amount of moles of solute in 200 cm3 of ammonia solution, having a concentration of 0.125 mol dm 3. Ans: (0.0250) Molal Concentration @ molality, m The number of mole of solute per unit mass of solvent in kg. (unit: mol kg 1 @ molal, m)

0.586 g N C a O
2

250.0 m L

1m N C ol a O
2

3 3

106 g N C a O
2

1000 m L 1.0 L

= 0.0221 mol

3) 4)

(b)

No. mole solute Mass of solvent in kg

1 kg

1000 g

Example 1.2.6: Calculate the molal concentration of ethylene glycol (C2H6O2) solution containing 8.40 g of ethylene glycol in 200 g of water. The molar mass of ethylene glycol is 62 g/mol. m (C2H6O2) = kg 1

8.40 g 200 g solvent

1m C H O ol
2 6

62 g

1000 g solvent 1.0 kg solvent

= 0.677 mol

15

Chapter 1: Matter

Note: Mass of solution = mass of solute + mass of solvent Volume of solution volume of solvent Exercise 1.2.4: 1) 2) 3) A mixture is prepared from 45.0 g of benzene, C6H6 and 80.0 g of toluene, C7H8. Calculate the molarity of the solution. [Ar C=12 ; H=1] Ans: (7.21m) A solution containing 121.8 g of Zn(NO3)2 per litre has a density of 1.107 g/mL. Calculate its molal concentration. [Ar Zn=65; N=14; O=16] Ans(0.654m) What is the molal concentration of a solution prepared by dissolving 0.30 mol of CuCl 2 in 40.0 mol of water? Ans(0.417m)

(c)

Weight Percent(% w/w) @ Percent by Mass

% w/w

Weight solute Weight solution

100%

10% w/w NaOH

10 g of NaOH dissolved in 100 g of solution

10 g of NaOH dissolved in 90 g of solvent (water)

Note: mass of solution = mass of solute + mass of solvent Example 1.2.7 : A sample of 0.892 g of potassium chloride, KCl is dissolved in 54.3 g of water. What is the percent by mass of KCl in this solution? Percent by mass of KCl = Exercise 1.2.5: 1) 2) Calculate the percent by mass of the solute in a aqueous solution containing 5.50 g of NaBr in 78.2 g of solution. Ans:(7.03) Calculate the amount of water (in grams) that must be added to 5.00 g of urea, (NH2)2CO in the preparation of a 16.2 percent by mass solution. Ans: (25.9) How many grams of NaOH and water are needed to prepare 250.0 g of 1.00% NaOH solution? Ans:(2.50; 248) Hydrochloric acid can be purchased as a solution of 37% HCl. What mass of this solution contains 7.5 g of HCl? Ans: (20.3)
0.892 g x 100% 0.892 g +54.2 g

= 1.61%

3)

4)

16

Chapter 1: Matter

(d)

Weight/volume percent (%w/v) % w/v = Weight of solute Volume of solution, mL 100%

5% w/v of KCl 5 g of KCl dissolved in 100 mL of solution Note: mass of solution = volume of solution x density of solution Example 1.2.8: What mass of NaCl is needed to prepare 250 mL of 0.9% w/v solution? 0.9% w/v NaCl =
mass of NaCl x 100% 250 mL solution

mass of NaCl = 2.25 g Exercise 1.2.6: Describe how to prepare a 10% w/v KOH solution.

(e)

Mole Fraction, X The mole fraction of component A is given by XA = n , where nA is the number of mole to l ta of one component in a mixture, A (for a given entity) and ntotal is the total number of mole of all substances present in the mixture (for the same entity).
n
A

nA ntotal

100%

ntotal = n A + n B +

Exercise 1.2.7: 1) 2) What is the mole fraction of CuCl2 in a solution prepared by dissolving 0.30 mol of CuCl2 in 40.0 mol of H2O? Ans:(0.0074) A solution is prepared by mixing 55 g of toluene, C7H8 and 55 g of bromobenzene, C6H5Br. What is the mole fraction of each component? Ans:(0.63; 0.37)

17

Chapter 1: Matter

3)

A mixture containing benzene and toluene has 18.4 g of toluene and its percentage composition is 30%. Calculate the number of moles of benzene in this solution. [Mr benzene = 78 and toluene = 92] Ans:(0.55)

(f)

Parts per million, ppm

Cppm

Weight solute weight solution Weight solute,mg Volume solution, L

100%

weight solute ppm = mg/L @ g /g @ g /mL @ mg / kg

Example 1.2.9: The concentration of calcium ions in blood is 100.0 ppm. Calculate the mass of calcium ions in 500.0 g of blood. 100.0 ppm =
m ass of Ca 2 + 500.0 g of solution x 10 6

mass of Ca2+ = 0.05 g Exercise 1.2.8: 1) 2) 3) What is the concentration of K+ in a solution that contains 63.3 ppm of K3Fe(CN)6? [relative formula mass of K3Fe(CN)6 = 329.3] Ans:(5.77x10 4) If the drinking water contains 1.5 ppm of NaF, how much water is needed to dissolve 454 g of NaF? Ans:(3.0x105L) A sample of 500 L of air has a density of 1.20 g dm 3 and it contains 2.40x10 3 g of SO2. Calculate the concentration of SO2 in the air in percent by mass and ppm. Ans:(4x10 4g,4ppm) A sample of drinking water was found to be severely contaminated with chloroform, CHCl3, a known carcinogen. The level of contamination was 12.4 ppm (by weight). a) Express this in percent by weight.

4)

18

Chapter 1: Matter

b)

What is the molar concentration of the CHCl3 in water?

1.2.3 Oxidation Number i) ii) For monatomic ions, the oxidation number is equal to the charge on the ion. For covalently bonded atom, the oxidation number is the charge on an atom calculated by assigning both electrons of a shared pair to the more electronegative atom.

Oxidation number signifies the number of charges the atom would have in a molecule (or an ionic compound) if electrons were transferred completely. Rules: 1) In free elements (that is, an element not combined chemically with a different element), each atom has an oxidation number of zero. Thus each atom in H2, Br2, Na, Be, P4 and O2 has the same oxidation number: zero. 2) For ions composed of only one atom (that is, monatomic ions) the oxidation number is equal to the charge on the ion. Oxidation number of Al3+ = +3 Ca2+ = +2 S2= 2
3)

The oxidation number of oxygen in most compounds (for example: MgO and H 2O) is 2, but in hydrogen peroxide (H2O2) and peroxide ion (O2
2

), it is 1.

4)

The oxidation number of hydrogen is +1, except when it is bonded to metals in binary compound. In these cases (for example: LiH, NaH, CaH2), its oxidation number is 1.

5) Fluorine has an oxidation number of 1 in all its compounds. Other halogens (Cl, Br, and I) have negative oxidation numbers when they occur as halide ions in their compounds. When combined with oxygen for example in oxoacids and oxoanions they have positive oxidation numbers.
6) 7)

In a neutral molecule, the sum of the oxidation numbers of all the atoms must be zero: CO2, FeSO4, NaCl. In a polyatomic ion, the sum of oxidation numbers of all the elements in the ion must be equal to the net charge of the ion: Cr2O72 , NO3 .

Example 1.2.10 : What are the oxidation number of a) Fe atom in FeCl3 b) Cr atoms in Cr2O72d) S atoms in Na2S4O6 e) N atom in NH4 + Oxidation number ( Ox.No.): a) +3 b) +6 c) (2 atoms)(Ox.No. of Cl) + 7(-2) = 0 (2 atoms)(Ox.No. of Cl) = +14 (Ox.No. of Cl)= +7 e) (Ox.No. of N) + 4(+1) = +1 (Ox.No. of N) = 3 c) Cl atoms in Cl2O7

d) +2.5

19

Chapter 1: Matter

1.2.4 Oxidation Number & Redox Reaction 1) Oxidation is an increase in oxidation number. 2) Reduction is a decrease in oxidation number. A substance is oxidized when it shows an increase in its oxidation number. This substance reacts as a reducing agent (reductant) in a chemical reaction. A substance is reduced when it shows a decrease in its oxidation number. This substance reacts as an oxidation agent (oxidant) in a chemical reaction.

Example 1.2.11:
increase, oxidation

decrease, reduction

0 H2

0 Cl2

+1 -1 2HCl

The hydrogen is oxidized (increased in oxidation number) and the chlorine is reduced (decreased in oxidation number). Thus, the reducing agent is H2 and the oxidizing agent is Cl2. Exercise 1.2.9: 1) Assign oxidation numbers to each of the following underlined elements: a) MnO4 MnO2 b) S2O32- SO42Identify the substance oxidized and the substance reduced as well as the oxidizing and reducing agents in the reaction: 2KCl + MnO2 + 2H2SO4 K2SO4 + MnSO4 + Cl2 + 2H2O

2)

1.2.5 Chemical Equation and Stoichiometry A chemical reaction is a process in which one set of substances called reactants is converted to a new set of substances called products. Chemical equation is a way of denoting a chemical reaction using the symbols for the participating particles (atoms, molecules, ions, etc.); formulae of the reactants are written on the left side of the equation and formulae of the products, on the right. xA + yB zC + wD ( ) is used for an irreversible reaction; double arrows ( reversible reactions.

) are used for

When reactions involve different phases it is usual to put the phase in brackets after the symbol (s = solid, l = liquid; g = gas; aq = aqueous).

20

Chapter 1: Matter

Because atoms can neither be created nor destroyed in a chemical reaction, the total number of atoms of each element is the same on both sides in a balanced equation. The numbers x, y, z, and w, showing the relative numbers of molecules reacting, are called the stoichiometric coefficients. Stoichiometry is the quantitative study of reactants and products in a chemical reaction. --- x moles of A react with y moles of B to yield z moles of C and w moles of D.

Example 1.2.12: CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g) + H2O(l) The chemicals reacting together and the chemicals produced. Reactants: CaCO3 and HCl Products: CaCl2; CO2; and H2O The physical states of reactants and products. The coefficients in a chemical equation provide the atom ratios or the mole ratios by which moles of one substance react with or form moles of another. 1 mole of CaCO3 reacts with 2 moles of HCl to yield 1 mole of CaCl2, 1 mole of CO2 and 1 mole of H2O. or 1 molecule CaCO3(s) + 2 molecules HCl(aq) 1 molecule CaCl2(aq) + 1 molecule CO2(g) + 1 molecule H2O(l) Symbol : irreversible reaction.

1.2.6 Balancing a Chemical Equation Method 1: By Inspection 1) 2) Write correct formulae for all reactants and products. Assign the most complex formula a coefficient of 1, Or if an element occurs in only one compound on each side of the equation, balance this element first, Or balance the atoms of each element (except H and O) The equation can be balanced only by adjusting the coefficients of the formulae, as necessary. Never introduce any species that are not involved in the reaction. Never change formulae for the purpose of balancing an equation. (consider polyatomic ions: 2 SO 2 , CO 3 , CN , etc. as one unit) 4 When one of the reactants or products exists as the free element, balance this element last. 3) 4) 5) 6) Then, work on the hydrogen and the oxygen. Check and make sure the total numbers of the atoms of each element is the same on both sides. Eliminate the fractional coefficient by multiplying a factor (an appropriate integer) on each coefficient in order to get the smallest set of whole number coefficients. The states of the reacting substances and products can be included in small brackets after the formulae.

Exercise 1.2.10:

21

Chapter 1: Matter

Balance the following chemical equations by applying inspection method. 1) 2) 3) 4) 5) NH3 + CuO Cu + N2 + H2O C6H6 + O2 CO2 + H2O AgNO3 + Na2CrO4 Ag2CrO4 + NaNO3 Fe(OH)3 + H2SO4 Fe2(SO4)3 + H2O N2O5 + H2O HNO3

Method 2: Algebraic Method (Mainly for the chemical equation that is difficultly balanced by inspection method) 1) Write correct formulae for all reactants and products. 2) Assign a stoichiometric coefficient (example: a, b, c and d) in front of each formula. 3) Form an algebraic equation, as there is the same number of atoms of each element indicated on both sides of the arrow. Use the elimination method to solve the algebraic equations. Assume a=1, then substitute this value into the algebraic equations to solve b, c and d. 4) Eliminate the fractional coefficient by multiplying a factor (an appropriate integer) on each coefficient in order to get the smallest set of whole number coefficients. Example 1.2.13: a Al2(SO4)3 + b KOH c Al(OH)3 + d K2SO4 a=1 c=2 b = 3(2) = 6 d = 3(1) = 3 2Al(OH)3 + 3K2SO4

Al : 2a = c if K : b = 2d then, OH : b = 3c SO4 : 3a = d The balanced chemical equation is: Al2(SO4)3 + 6KOH

For element:

Exercise 1.2.11: Balance the following chemical equations by applying algebraic method. 1) 2) N2H4 + ClO2 + H2O2 H2O HNO3 + HClO3 + H2O HCl

Method 3: The Ion Electron Method (Mainly for balancing the oxidation reduction equations) Reactions that involve both REDuction and OXidation are called REDOX reactions Oxidation is an Increase in the oxidation number and the substance Loses one or more electrons (OIL). Reduction, conversely, is the process in which some substance gains one or more electrons and the oxidation number of an atom in that substance decreases. Oxidation Agent (Oxidant): A substance that gains electrons and brings about oxidation in other substances. Reducing Agent (Reductant): A substance that loses electrons and brings about reduction in other substances.

22

Chapter 1: Matter

The sequence of steps used in balancing a redox equation in acidic solution is as follows: 1) Identify the oxidizing agent and its reduced form as well as the reducing agent and its oxidized form, and write two skeletal half-reaction. 2) In each half-reaction, balance the atoms of the elements undergoing changes in oxidation number. 3) Balance oxygen atoms by using H2O. 4) Balance hydrogen atoms by using H+(aq). 5) Balance the charge in each half-reaction by adding electrons to equalise the ionic charges. The number of electrons to be added is determined without reference to the oxidation number. Electrons are added simply to balance the charge. 6) Multiply the half-reactions by appropriate integers to ensure that the number of electrons lost in oxidation is equal to the number of electrons gained in reduction. 7) Sum the half-reaction. Simplify the overall equation algebraically so that any H 2O or H+(aq) appears on only one side of the equation. Check the charge balance as well as the balance of all atoms. [Balancing the redox reactions in basic solution: Balance the equation first as if the solution were acidic, and then add enough OH to both sides of the equation balanced so that wherever + H (aq) appears, it can be combined with OH to form H2O. The number of hydroxide ions added is equal to the number of hydrogen ions in the equation. Be sure to combine H2O if it appears on both sides of the equation.] Exercise 1.2.12: Balance the following chemical equations by applying the ion-electron method. 1. 2. MnO + 4 Cr2O
2 7

C2O 2 + 4 Fe2+ +
+

H+ H+

Mn2+ Cr3+ +
2 4 2

CO2 + H2O (acidic solution) H2O (acidic solution) (acidic media) (basic media) (basic
2+

Fe3+ +

3. MnO + SO2 + H SO + 4. Cr(OH)3 + IO3 + OH CrO3 + 2 2 S 2 O3 SO 4 5. ClO + Cl + media) ClO 3 + 6. Cl2 Cl NO 3 + 7. NO2 NO 2+ 8. P + Cu Cu3P + H3PO3 1.2.7 Stoichiometric calculations and limiting reactant

Mn + H2O I + H2O

When all the reactants are completely and simultaneously consumed in a chemical reaction, they are exactly in stoichiometric proportions/amounts (the proportions indicated by the balanced equation). However, some reactions proceed better when one reactant is in stoichiometric excess. Therefore, in many situations a chemist deliberately mixes reactants in a mole ratio that does not agree with the coefficients of the equation. In this sense, the reactant that is completely consumed first (the limiting reagent) determines the amount of products that form.
System (before the reaction) System (after the reaction)

23

Chapter 1: Matter

Limiting reactant

Excess Reactant

Product

Balance d

Excess Reagents are the reactants present in quantities greater than necessary to react with the quantity of the limiting reagent. The concept of the limiting reagent is analogous to the relationship between men and women in a dance contest at a club. If there are fourteen men and only nine women, then only nine female/male pairs can compete. Five men will be left without partners. The number of women thus limits the number of men that can dance in the contest, and there is an excess of men. In stoichiometric calculations involving limiting reagents, the first step is to decide / identify which reactant is the limiting reagent. Then, calculate the amount of product formed based on the amount of the limiting reagent available. Notes: 1) 2) 3) 4) The first step in a stoichiometric calculation is to write a balanced equation. Either this must be given or you must be able to supply your own. The coefficients in the balanced equation tell you only the molar ratios in which the species combine or are formed. Always base the calculation of the maximum yield of product on the stoichiometric equivalency (molar ratio) between it and the limiting reagent. To identify the limiting reagent:

The limiting reagent is the reactant with the smallest ratio of the number of moles the stoichiome tric coefficien t

Example 1.2.14: Urea [(NH2)2CO] is prepared by reacting ammonia with carbon dioxide: 2NH3(g) + CO2(g) (NH2)2CO(aq) + H2O(l) In one process, 637.2 g of NH3 are allowed to react with 1142 g of CO2. a)Which of the two reactants is the limiting reagent? b) Calculate the mass of (NH2)2CO formed. c)How much of the excess reagent (in grams) is left at the end of the reaction? a) Since we cannot tell by inspection which of the two reactants is the limiting reagent, we have to proceed by first converting their masses into numbers of moles. Moles of NH3 = 637.2 g NH3 x 17.03 g N H Moles of CO2 = 1142 g CO2 x
1m C ol O
2 2

1ml N o H

3 3

= 37.42 mol NH3 = 25.95 mol CO2

44.01 g C O

Method 1: The balanced equation shows that 2 mol NH 3 1 mol CO2; therefore, the number of moles of NH3 needed to react with 25.95 mol CO2 is given by 25.95 mol CO2 x
2m N ol H 1 m CO ol
3 2

= 51.90 mol NH3

24

Chapter 1: Matter

Since there are only 37.42 moles of NH3 present, not enough to react completely with the CO2, NH3 must be the limiting reagent and CO2 the excess reagent. Method 2: ratio of
the number of moles the stoichiome tric coefficien t

for NH3:

37 .42 = 18.71 2

for CO2:

25 .95 = 25.95 1

Since the NH3 has the smallest ratio, NH3 is the limiting reagent. To calculate the maximum yield of (NH2)2CO formed, we must based on the stoichiometric proportions (the proportions indicated in the balanced equation) between the product and the limiting reagent, NH3. The balanced equation shows that 2 mol NH3 1 mol (NH2)2CO
b)

Mass of (NH2)2CO = 37.42 mol NH3 x = 1124 g (NH2)2CO c)

1 m (N ol H

) C O
2 3

2m N ol H

60.06 g (N H 1 m (N ol H

) C O
2

) C O
2

Since NH3 is the limiting reagent, CO2 must be the reactants left over after the reaction is finished. The difference between the amount of CO2 available and the amount consumed is the amount left over. The number of moles of CO2 (the excess reagent) left over is 25.95 mol CO2 (37.42 mol NH3 x 2 m N ol H
1m C ol O
2 3

) = 7.24 mol CO2

44 .01 g C O
2 2

mass of CO2 left over = 7.24 mol CO2 x 1 m C ol O g CO2 Exercise 1.2.13: 1)

= 319

The reaction between aluminium and iron (III) oxide can generate temperatures approaching 3000C and is used in welding metals: 2Al + Fe2O3 Al2O3 + 2Fe In one process 124 g of Al are reacted with 601 g of Fe2O3. a) Identify the limiting reagent. b) Calculate the mass (in grams) of Al2O3 formed. c) How much of the excess reagent (in grams) is left over at the end of the reaction? Aluminium, Al reacts with sulphuric acid, H2SO4, which is the acid in automobile batteries, according to the equation: 2Al + 3H2SO4 Al2(SO4)3 + 3H2 If 20.0 g of Al is put into a solution containing 115 g of H2SO4, a) Which reactant will be used up first? (Ans:Al) b) Calculate the number of moles of Al2(SO4)3 will be produced? (Ans:1.11 mol) c) How many grams of Al2(SO4)3 can be formed? (Ans:127 g) d) Calculate the mass (in grams) of the excess reagent remaining at the end of the reaction. (Ans: 6 g) Hydrazine, N2H4 and hydrogen peroxide, H2O2 are used as rocket reagent in which the mixture of these two substances will produce nitric acid, HNO3 and water. a) Write a balanced chemical equation for this reaction. b) How many moles of HNO3 will be formed from 3.5 g of N2H4? (Ans:0.22 mol) c) Calculate the number of moles of H2O2 required to react with 22.0 g of N2H4? d) (Ans: 4.81 mol)

2)

3)

25

Chapter 1: Matter

e)

f)

How many moles of HNO3 are produced when 30.5 g H2O2 is allowed to react with 25.6 g of N2H4? Which compound is the limiting reagent? (Ans:0.256 mol) How many grams of the reactant in excess remain after the reaction is completed? (Ans:21.5 g)

Reaction yield and percentage yield The amount of limiting reagent present at the start of a reaction determines the theoretical yield of the reaction, that is, the amount of product that would result if the entire limiting reagent reacted. The theoretical yield, then, is the maximum obtainable yield, predicted by the balanced equation. In practice, the actual yield, or the amount of product actually obtained from a reaction. There are several reasons for the difference between actual and theoretical yield: 1. Side reaction may occur, that is other reactions in addition to the principle one may take place. 2. Procedures may be necessary to separate the product from the reaction mixture and obtain it in a pure state. Product may be lost during the separation and purification processes. 3. The reaction may not go to completion. 4. There may have been impurities in one or more of the reactants. To determine how efficient a given reaction is, chemists often figure the percentage yield, which describes the proportion of the actual yield to the theoretical yield.
actual yield x 100% theoretica l yield

% yield =

Exercise 1.2.14: 1) Chlorofluorocarbons, commonly known as Freons, have been implicated in the gradual destruction of the earths ozone shield. One of these, Freon-12 (CCl2F2), is a gas that is used as a refrigerant and is prepared by the reaction: 3CCl4 + 2SbF3 3CCl2F2 + 2SbCl3 In a certain experiment, 14.6 g of SbF 3 was allowed to react with an excess of CCl 4. After the reaction was finished, 8.62 g of CCl2F2 was isolated from the reaction mixture. a) What was the theoretical yield of CCl2F2 in this experiment expressed in grams? (Ans:14.8g) b) What was the actual yield of CCl2F2 in grams? (Ans:8.62g) c) What was the percentage yield of CCl2F2 in this experiment? (Ans:58.2%) 2) In an experiment, a student allowed benzene, C6H6 to react with excess bromine, Br2 in an attempt to prepare bromobenzene, C6H5Br. This reaction also produced, as a by-product, dibromobenzene, C6H4Br2. On the basis of the equation: C6H6 + Br2 C6H5Br + HBr

26

Chapter 1: Matter

a) What is the maximum number of grams of C6H5Br that the student could have hoped to

obtainfrom 15.0 g of benzene? (Ans:30.1 g) b) In this experiment, the student obtained 2.50 g of C6H4Br2. How many grams of C6H6 were not converted to C6H5Br? (Ans:0.828 g) c) What was the students actual yield of C6H5Br in grams? (Ans:28.5 g) d) Calculate the percentage yield for this reaction. (Ans:94.7%) 3) A chemist wishes to synthesize a certain compound that has a molecular mass of 100. The synthesis requires six consecutive steps, each giving a 50% yield (computed on a mole basis). If the chemist begins with 30.0 g of starting material having a molecular mass of 80.0, how many grams of final product will be obtained? How many grams of starting material will be required to produce 10.0 g of final product. (Ans:0.590g; 508g) 4) Industrially, vanadium metal, which is used in steel alloys, can be obtained by reacting vanadium(V) oxide with calcium at high temperatures: 5Ca + V2O5 5CaO + 2V In one process 1.54 x 103 g of V2O5 react with 1.96 x 103 g of Ca. a) Calculate the theoretical yield of V. g) b) Calculate the percent yield if 803 g of V are obtained.

(Ans:863 (Ans:93.0 %)

5) Ethylene, C2H4 an important industrial organic chemical, can be prepared by heating hexane, C6H14 at 800C: C6H14 C2H4 + other products If the yield of ethylene production is 42.5%, what mass of hexane must be reacted to product 481g of ethylene? (Ans:3.47x103 g) 1.2.9 Stoichiometry of reactions in solution (a) Dilution of solution Dilution is a procedure for preparing a less concentrated solution from a more concentrated one. All the solute in the initial more concentrated solution, appears in the final diluted solution.
Vf

Dilution
Vi ci

Volume of water (solvent) added

cf

moles of solute before dilution = moles of solute after dilution Notes: Adding more solvent to a given amount of the stock solution changes (decreases) the concentration of the solution without changing the number of moles (or mass) of solute present in the solution.

27

Chapter 1: Matter

ni

Molarity, M =

n ; V in litre/dm3 V

M i Vi = M f V f

i = initial concentrated solution f = final diluted solution

Example 1.2.15: A particular analytical chemistry procedure requires 0.0500 M K2CrO4. What volume of 0.250 M K2CrO4 must be diluted with water to prepare 100 mL of 0.0500 M K2CrO4.
M
V
f

= 0.0500 M

= 0.250 M
V
i

= 100.0 mL (0.0500 M)(100 mL)

V
i

=?
V
i

= (0.250 M) = 20.0 mL

The laboratory procedure for preparing a solution by solution is as follow: A pipette is used to withdraw a 20.0 mL sample of 0.250 M K2CrO4(aq). The pipetteful of 0.250 M K2CrO4 is discharged into a 100.0 mL volumetric flask. Following this, water is added to bring the level of the solution to the calibration mark etched on the neck of the flask. At this point the solution is 0.0500 M K2CrO4.

Exercise 1.2.15: 1) 2) 3) 4) When left in an open beaker for a period of time, the volume of 275 mL of 0.105 M NaCl is found to decrease to 237 mL. What is the new concentration of the solution? Distilled water is added to a 25.0 mL of 0.866 M KNO3 so that the final volume is brought up to 500 mL. What is the new concentration of this solution? (Ans:0.0433M) You have a solution of 505 mL 0.125 M HCl and you would like to dilute it to 0.100 M. What volume of water should you add? (Ans:126mL) A solution of 46.2 mL 0.568 M calcium nitrate, Ca(NO3)2 is added to a solution of 80.5 mL 1.396 M calcium nitrate. What is the final concentration of the mixture? (Ans:1.09M)

(b) Titration / Titrimetric analysis / titrimetry The titration is a method of volumetric analysis in which a volume of one reagent (the titrant) is added slowly (from burette) through the stopcock into another vessel (conical flask) that contains a known volume of another reagent (analyte). The trick is to stop the titration at the point where both reactants (titrant and analyte) have been consumed simultaneously, a condition called the equivalence point of the titration.

28

Chapter 1: Matter

In a titration we need some means of signalling when the equivalence point is reached. A small quantity of indicators added to the reaction mixture and it changes colour at or very near the equivalence point. The point at which an excess one-drop of titrant changes the colour of the indicator is called the end point of the titration - the delivery of the titrant is stopped and the volume of the titrant used in the reaction recorded. Given the concentration of one (standard solution), the aim is to find the concentration of the other. analyte + titrant product

Titrant: : concentration of titrant : volume of added titrant or titre value

Calculations:

M t Vt = stoichiometric M aV a
proportions

Analyte: : concentration of analyte : volume of pippeted analyte

Types of Titration: i. Acid-base titrations ii. Redox titrations iii. Back titrations (i) Acid-Base Titrations Reaction between acid and base Example 1.2.16: How many millilitres of 0.112 M HCl will react exactly with the sodium carbonate in 21.2 mL of 0.150 M Na2CO3 according to the following equation? 2HCl(aq) + Na2CO3(aq) 2NaCl(aq) + CO2(g) + H2O(l) = 0.112 M HCl V =? a
a

= 0.150 M Na2CO3 V = 21.2 mL Na2CO3 b

The balanced equation shows the stoichiometric ratio is 2:1.

c V
a a

c V
b

2 1

(0.112 M V ) (0.150 M )(21.2

V
a

m L)

2 1

= 56.8 mL HCl soln

Exercise 1.2.16: 1) In a titration between 20.0 cm3 standard solution of sodium carbonate and HCl, it needs 19.15 cm3 of HCl for neutralization. If the concentration of Na 2CO3 is 0.052 M, calculate the concentration of HCl. (Ans:0.109M)

29

Chapter 1: Matter

2)

0.321 g sample of sodium carbonate, contaminated by sodium chloride, was dissolved in water. The resulting solution required 35.4 mL of 0.144 M HCl to react completely with the sodium carbonate. (The impurity does not interfere.) The products of the reaction are sodium chloride, carbon dioxide and water. a) Write the balanced equation for this reaction. b) How many grams of sodium carbonate were in the sample? (Ans:0.270g) c) Calculate the percentage of sodium carbonate in the sample. (Ans:84.1% ) Calculate the volume of 0.12 mol dm 3 KOH required to react with 25.0 cm3 of H3PO4 solution according to the equation: 2KOH + H3PO4 K2HPO4 + 2H2O The H3PO4 solution contains 4.90 g of H3PO4 per dm3. [H=1.00; O=16.0; P=31.0] (Ans:20.8cm-3) A sample of analgesic drug was analyzed for aspirin, a monoprotic acid, HC 9H7O4, by titration with a base. In a titration, a 0.500 g sample of the drug required 21.50 mL of 0.100 M NaOH for complete neutralization. What percentage by mass of the drug was aspirin? (Ans:77.4%) 5.125 g of washing soda crystal are dissolved and made up to 250 cm3 of solution. A 25.0-cm3 portion of the solution requires 35.8 cm3 of 0.0500-mol dm 3 sulphuric acid for neutralization. Calculate percentage of sodium carbonate in the crystal. (Ans:37.1%) Sodium carbonate crystal (27.8230 g) were dissolved in water and made up to 1.00 dm 3. 25.0 cm3 of the solution were neutralized by 48.8 cm3 of hydrochloric acid of concentration 0.100 mol dm 3. Find n in the formula Na2CO3.nH2O. (Ans: 10) 0.960 g of zinc is dissolved in 50.00 cm3 of 1.04 M HCl solution. The final volume is brought up to 250 cm3 by adding water. In a titration, 20.0-cm3 portion of the solution is completely neutralized with 17.20 cm3 of 0.105 M NaOH. What is the atomic mass of zinc? (Ans:65.3)

3)

4)

5)

6)

7)

(ii) Redox titration Reactions between oxidants and reductants.

2 r In a redox titration that involves permanganate ion, MnO or dichromate ion, C 2 O 7 , no 4 indicator is needed in the reaction as these ions have an obvious different colour between the ions and their reduced form.

acid media MnO 4 Mn2+

(purple)
MnO 4 base media

(colourless) MnO2 (p) (brown) Cr3+ (green)

(purple)
2 C 2 O7 acid media r (orange)

2 For the redox reaction between I2 and S 2 O3 , starch solution is added near the end point as an indicator for the redox titration.

30

Chapter 1: Matter

Example 1.2.17: A 16.42-mL volume of 0.1327 M KMnO4 solution is needed to oxidize 20.00 mL of a FeSO4 solution in an acidic medium. What is the concentration of the FeSO 4 solution? The net ionic equation is
5Fe2+ + MnO 4 + 8H+ Mn2+ + 5Fe3+ + 4H2O

The balanced equation shows the stoichiometric proportion is 5:1 (5 mol Fe2+ 1 mol MnO 4 ).

M
V
f

(Fe2+) = ?

M m ( MnO 4 ) = 0.1327 M

= 20.00 mL M fVf 5 = M mV m 1

= 16.42 mL M f (20 .00 mL) 5 = (0.1327 M )(16.42 mL) 1

m

= 0.5450 M

Exercise 1.2.17:
1)

How many millilitres of a 0.206 M HI solution are needed to reduce 22.5 mL of a 0.374 M KMnO4 solution according to the following equation: 10HI + 2KMnO4 + 3H2SO4 5I2 + 2MnSO4 + K2SO4 + 8H2O (Ans:204 mL) In a titration, 25.00 cm3 of H2O2 solution is needed to react completely with 35.00 cm 3 of 0.02 M KMnO4 solution. Calculate the concentration of H2O2 solution. (Ans:0.07M) Ammonium iron(II) sulphate crystals have the following formula: (NH4)2SO4.FeSO4.nH2O. In an experiment to determine n, 8.492 g of the salt were dissolved and made up to 250 cm 3 of solution with distilled water and dilute sulphuric acid. A 25.0 cm3 portion of the solution was further acidified and titrated against potassium manganate(VII) solution of concentration 0.0150 mol dm 3. A volume of 22.5 cm3 was required. (Ans:12) Vanadium(II) ions can be oxidised quantitatively by acidified manganate(VII) ions, to a higher oxidation number. Two half-equation for the reaction can be written: V2+ Vz+ + (z 2)e + MnO4 + 8H + 5e Mn2+ + 4H2O In an experiment, 25.0 cm3 of 0.02 moldm 3 V2+ was found to react with 15.0 cm3 of 0.02 mol 3 dm MnO4 , acidified with sulphuric acid. a) How many moles of V2+ were used in the titration? (Ans:0.0005 mol) b) How many moles of MnO4 were used in the titration? (Ans:0.0003 mol) c) How many moles of V2+ reacted with one mole of MnO4 ? (Ans:5/3 mol) 2+ d) Hence deduce the number of electrons given up by one V ion when it is oxidised. (Ans:3) e) What is the new oxidation number of vanadium after oxidation (ie what is z)? Ans:(+5) An amount of a solution containing 0.092 M of iron(II) requires 21.7 cm3 of M2Cr2O7 solution with a concentration of 4.63 g/dm3 for complete oxidation. Determine the relative atomic mass of M. (Ans:23)

2) 3)

4)

5)

31