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# Chapter 1 Matter

## THE STRUCTURE OF ATOM

j 3 fundamental particles of matter are the proton, neutron and electron j Proton number and nucleon number j a symbol below is used to designate a particular atom of an element where X is the symbol of the element, A is the nucleon number (or mass number) and Z is the proton number (or atomic number)
A Z

j the nucleon number is the sum of the number of protons and neutrons in the nucleus of an atom. j the proton number is the number of protons present in the nucleus of an atom. j in neutral atom, the number of protons is equal to its number of electrons.

ISOTOPES
j isotopes are atoms of the same element with the same proton number but different nucleon numbers. The atoms have different number of neutrons. j for example: j hydrogen has 3 isotopes Hydrogen,
1 1

Deuterium,
2 1

Tritium,
3 1

## 1 proton 1 electron 2 neutrons

j isotopes of an element have the same : j proton number j number of electrons in a neutral atom j electronic configuration j chemical properties j isotopes of an element have different: j number of neutrons in the nucleus j mass j density j rate of diffusion

RELATIVE MASSES
j Relative Isotopic Mass j the relative isotopic mass of an isotope is the ratio of the mass of one atom of the isotope the one-twelfth of the mass of an atom of the mass of an atom of the 12C isotope Mass of one atom of isotope Relative isotopic mass = 1/12 x mass of one atom 12C

j Since the relative masses of the proton (1.0074 a.m.u) and the neutron (1.0089 a.m.u) are both very close to one another and the electron has negligible mass, it follows that all relative isotopes masses will be very close to whole numbers. j the relative isotopic mass of an isotope can be assumed to be identical to its nucleon number.

j Relative Atomic Mass j the relative atomic mass (Ar) of an element is the average mass of all the isotopes of the element weight to take into account the neutral relative abundances of the isotopes, compared to one-twelfth of the mass of an atom of the 12C isotope.
Relative atomic mass = Weighted average mass of the atom 1/12 x mass of one atom 12C

j Relative Molecular Mass (Mr) and Relative Formula Mass j the relative molecular mass (Mr) of a compound is the ratio of the mass of one molecular of the compound to one-twelfth of the mass of an atom of the 12C isotope.
Mass of one molecule of the compound Relative molecular mass = 1/12 x mass of one atom 12C isotope

j for ionic compounds, which do not consists of molecules, the term relative formula mass is used instead.

## j Molar Mass (M)

j the molar mass (M) of a substance is the mass of one mole of the substance as specified by its chemical formula. It has the units g mol-1

j example: jcalculate the molar mass of Na jM of Na = 23.0 g mol-1 jcalculate the molar mass of CH3Cl jM of CH3Cl = 12.0 + 3(1.0) + 35.5 j 50.5 g mol-1

MASS SPECTROMETRY
U The mass spectrometer U the mass spectrometer is an instrument used: U to determine the relative isotopic masses and abundances of isotopes. U to determine the relative molecular masses and structure of organic compounds. U the mass spectrometer works on the principle that when ions or charged particles pass through a magnetic field, they will be separated according to their mass (m) ratio Charge (e)

## The mass spectrometer

recorder

U the sample to be studied undergoes five separate stages once it has been injected into the mass spectrometer: U Vaporisation = the sample is vaporised U Ionisation = positive ions are produced from the sample U Acceleration = the positive ions produced are accelerated by an electric field U Deflection = the positive ions are deflected by a magnetic field U Detection = the positive ions are detected and a record is made

## U Vaporisation U the sample must be in gaseous form, liquids

and solids are heated to vapourised them. U for example: X(s) X(g) X(l) X(g) U the vapour formed is then injected directly into the ionisation chamber

## U Ionisation U the ionisation chamber, the sample is

bombarded with high-energy electrons produced by the electron gun to cause ionisation. U electrons from the sample are knocked out by the high-energy electrons and hence positive ions are produced X(g) + e- X+ + 2e-

## U Acceleration U the positive ions produced are accelerated

by using and electric field with a high negative potential applied across parallel plates. U the ions are focused to produce a narrow beam when they pass through slits in these plates

## U Deflection U the accelerated ions are passed through a

magnetic field where they are deflected. U the amount of deflection depends on their mass ratio

charge U Detection
U ions that reach the detector produce a

current. U this current is amplified and a record, the mass spectrum of the sample, is obtained

## MASS SPECTRUM QUESTION PATTERN

The mass spectrum shows that the element consists of three isotopes with relative masses m1, m2 and m3 in the ration of b : a : c , the relative atomic mass (Ar) or the element can be calculated from the formula below:
c

## Ar = (m1 x b) + (m2 x a) + (m3 x c) a+b+c

b a

m1

m2

m3

The mole concept and Avogadro Constant U a mole is the amount of substance that contains as many particles (atoms, molecules or ions as specified by the formula) as there are carbon atoms is 12 kg of carbon-12. U the number of particles in 1 mol of any substance is a constant known as the Avogadro's constant (L) = 6.02 x 1023 mol-1 U the mass of 1 mol of any substance is the same as the relative atomic mass, or relative molecular/formula mass of that substance expressed in gram

U EXAMPLE: (1.9 PAGE 17) U Determine the number of atoms in each of the following substances (a) 1 mol of magnesium (b) mol of oxygen gas (c) 3 mol of carbon dioxide

U ANSWER: (1.9 PAGE 17) (a)1 mol of Mg contains 6.02 x 1023 atoms (b) mol of oxygen gas = x 6.02 x 1023 molecules of O2 = 2 x (1/2 x 6.02 x 1023) atoms oxygen = 6.02 x 1023 atoms (c) TRY YOURSELF

Moles of gases UIn reactions involving gases, the volume of the gases that take part in the reaction is usually more important than the mass of the gases involved. UThe relationship between the amount of gas (number of moles of gas) and the volume of gas is given in Avogadros law. UAvogadros law = under the same conditions of temperature and pressure, equal volume of gases contain equal number of moles Volume number of moles

UExample: Under room conditions, 10 cm3 of CO2 will contain the same number of moles or molecules as 10 cm3 of N2 UAt standard temperature and pressure (s.t.p; 273 K and 101 kPa), 1 mol of all gases will occupy a volume of 22.4 dm3. this volume is known as the molar volume (Vm). UUnder room conditions, 1 mol of all gases occupies 24.0 dm3

## Reacting Volumes of Gases Standard Temperature and Pressure

U when stating the volume of gas, the temperature and pressure at which the volume was measured must be stated. U the conditions of standard temperature and pressure (s.t.p) are temperature of 0oC (273 K) and 1.0 atmospheric pressure (1.01 x 105 Nm-2) U at s.t.p one mole of gas occupies 22.4 dm3

Standard conditions U standard conditions should not be confused with standard temperature and pressure (s.t.p) U under standard conditions, gases are at a pressure of 1 atm (1.01 x 105 Nm-2), solutions are at unit concentration (1.0 mol dm-3) and the temperature must be specified. If the temperature is not stated, then it is assumed to be 298 K (25oC)

UQUESTIONS: Calculate the volume occupied by the following gases at room conditions (a) 40 g of NH3 (b) 1.5 g of CO2 23 molecules of O (c) 24 x 10 2

UANSWERS: (a) 40 g NH3 = 40 mol of NH3 17 Volume = 40/17 x 24 dm3 Volume = 56.47 dm3 for questions (b) and (c) try yourself Answers: (b) 0.818 dm3 (c) 96.0 dm3

UEXERCISES: 1. Calculate the mass of methane gas, CH4, which will occupy the same volume as 8.0 g of nitrogen gas under the same conditions 2. The equation for the complete combustion of methane is CH4(g) + 2O2(g) CO2 (g) + 2H2O(g) What volume of oxygen gas is required to completely burn 60.0 cm3 of methane under the same conditions?
Page 18 pre-u text physical chemistry

## Moles And Solutions

U the concentration of a solution is usually expressed as the mass of solute per 1.0 dm3 of solution (g dm-3) or expressed as the number of moles of solute in 1 dm3 of solution (mol dm-3) UThe concentration in the unit of mol dm-3 is also known as the molarity of the solution (symbol: M)

## Moles And Solutions

Molarity, M (mol dm-3) = -3) Concentration (g dm Molar mass of the solute (g mol-1)
The number of moles of solute present in a given volume of a solution (of molarity M) is Number of moles of a solute = molarity x volume (in dm3)

(1) Calculate the molarity of a solution containing 7.3 g HCl in 1 dm3 of solution. (2) Calculate the concentration (in g dm-3) in a solution of 0.24 M sodium nitrate. (3) Calculate the molarity of sodium hydroxide which contains 23.0 g NaOH in 250 cm3 of solution (4) Calculate the number of moles of copper sulphate in 400 cm3 of 0.50 M CuSO4 solution (5) Calculate the number of ions in 250.0 cm3 of 0.3 M aqueous aluminium chloride

## U the concentration of a solution is given by

c = n/V
WHERE: c = concentration (mol dm-3) n = amount of solute (mol) V = volume (dm3)

## Number of moles = MV/1000

WHERE: M = molarity (mol dm-3) V = volume (cm3)

EXAMPLE: U a solution Cl was prepared by dissolving 0.429 g of a base A(OH)2 into 500 cm3 of 0.10 mol dm-3 sodium hydroxide. 25.0 cm3 of Cl required 23.10 cm3 of 0.12 mol dm-3 hydrochloric acid for complete neutralisation. (a)calculate: (i) The concentration of OH- (in mol dm-3) in Cl (ii) The number of moles of A(OH)2 in Cl (iii)The relative atomic mass of A (b)Deduce what A is

## (a)(i) OH-(aq) + H+(aq)

H2O(l)

MOH- VOH= MH+ VH+ MOH- x 25.0 = 0.12 x 23.10 MOH- = 0.11 mol dm-3

(a) (ii) total number of moles of OH- in 500 cm3 of Cl MV/1000 = 0.11 X 500 = 0.055 mol 1000 Number of moles of OH- from NaOH present in Cl MV/1000 = 0.10 X 500 = 0.050 mol 1000 Number of moles = total number of - number of moles of of OH- from A(OH)2 moles of OHOH- from NaOH =0.055 0.050 = 0.005 mol

(a) (iii) A(OH)2(aq) A2+(aq) + 2OH-(aq) 2 mol of OH- is obtained from 1 mol of A(OH)2. So 0.005 mol of OH- is obtained from: 0.005 x 1 = 0.0025 mol of A(OH)2 2 Number of moles 0.0025 = m/M = 0.429/M = 171.6 g mol-1 Molar mass of A(OH)2 = Ar of A + 2(16 + 1) Ar of A = 171.6 - 2(17) Ar of A 138 (b) A is Barium, Ba

## Empirical Formula and Molecular Formula

U the empirical formula of the compound shows the simples whole number ratio for the atoms of all the different element present in one molecule of the compound. U the molecular formula of a compound shows the actual number of atoms of different elements in one molecule of the compound.

Compound
Ethane Phosphorus (V) oxide

Molecular formula

Empirical formula

## CH2 P2O5 HO CH2O

Hydrogen peroxide

Ethanoic acid

Example:
U a hydrocarbon has the following composition by mass: C = 92.3%; H = 7.6% (a) calculate its empirical formula (b) given that the Mr for the hydrocarbon is 78, determine its molecular formula

## Question from the pre-u text stpm longman page 21

Elements present Mass per 100 g of compound Number of moles Simplest mole ratio carbon 92.3 g 92.3/12 = 7.7 7.7/7.6 1 hydrogen 7.6 g 7.6/1 = 7.6 7.6/7.6 = 1

The empirical formula is CH (b) Let the molecular formula be (CH)n Mr of compound = (12 + 1)n = 13n 13n = 78 n = 78/13 = 6 molecular formula is C6H6

EXERCISES:
A compund Y has the following composition by mass: Na, 29.1% ; S, 40.5% ; O, 30.4% Calculate the empirical formula of Y

## Question from the pre-u text stpm longman page 21

COMBUSTION DATA
UThe empirical formula or molecular formula of a compound can also be determined by the combustion data when the compound is burnt completely in oxygen.

Example:
When 10.8 g of magnesium is completely burnt in excess oxygen, 18.0 g of an oxide is formed. Determine the empirical formula of the oxide

## Question from the pre-u text stpm longman page 22

Mass of oxygen combined with 10.8 g of Mg = 18.0 g 10.8 g = 7.2 g Composition by mass of oxide is 10.8 g Mg : 7.2 g O Mole ratio of Mg : O = 10.8/24 : 7.2/16 = 0.45 : 0.45 = 1:1 Empirical formula is MgO
Question from the pre-u text stpm longman page 22

Exercises:
1. 100 cm3 of gaseous hydrocarbon requires 450 cm3 of oxygen for complete combustion to give 300 cm3 of carbon dioxide. All volumes are measured under the same conditions. Calculate the molecular formula of the hydrocarbon.

Gas Laws

## The kinetic theory OF MATTER

* the kinetic theory describes the behavior of particles in solids, liquids and gases. * this theory is based on the following assumptions: *The Solid State *The particles are held rigidly in fixed positions by strong attractive forces in an orderly arrangement *The particles cannot move freely from one location to another, they can only vibrate or rotate about their position *Not easily compressed *Have fixed shaped and fixed volumes *Have less energy compared to liquids and gaseous

*The Liquid State *Forces holding the particles together are weaker than those holding the particles together in the solid state *Packed closely together in clusters *Not in an orderly arrangement *Particles can vibrate, rotate and move freely throughout the liquid *Not easily compressed *Have no fixed shape (take the shape of the container) but have no fixed volume *The particles in liquids have more energy compared to particles in solid but have less energy that those in gases.

*The Gaseous State *Composed of atoms or molecules that are separated from each other by distances far greater than their own size *Can be considered as point particles, that is they possess mass but have no volume *No forces between the gas particles *The particles can vibrate, rotate and move anywhere within the container where the gas is placed *Easily compressed *Gas are in constant random motion, moving in straight lines unless they collide with the walls of container or with other gas particles

*When the particles collide with the walls of the container, they exert a pressure on the container *Collision are perfectly elastic, no loss of kinetic energy during collisions *Average kinetic energy of the particles is directly proportional to the absolute temperature of the gas (Kelvin scale)

## Boyles Law: The relationship of the volume of a gas

* Boyles law states that the pressure of a fixed mass of gas at a constant temperature is inversely proportional to its volume. * Mathematically, the law may be expressed as:

P
* Putting it in equation:
P = V k

1 V

## * From this relationship, we can deduce that:

PV = constant or PV = k (At the constant mass and temperature)

P1V1 = P2V2

* Boyles law can be presented by the following graphs at fixed mass and constant temperature

* according to Boyles Law, when the pressure acting on the gas is increased, its volume will decrease. As pressure is increased to infinity, 1/p approaches zero and the volume of the gas is reduced to zero. *A gas which obeys Boyles Law perfectly under any condition is known as an ideal gas or a perfect gas, a gas which exists only in theory * *However, all real gases (eg: Nitrogen, carbon dioxide, chlorine, oxygen, ect) do not obey Boyles Law perfectly, especially under high pressure and low temperature.

*This is because at high pressure, the gas particles are very close to one another, and the intermolecular attractive forces are strong enough to cause the gas to condense into liquid. *For a gas to obey Boyles Law perfectly under any condition, the gas particles must have zero volume (so that at infinite pressure, the volume occupied by the gas will become zero), and there must not be any intermolecular forces between the gas particles(so that the gas does not condense due to any intermolecular attractive force)

EXERCISES: A 1.00 L sample of gas at atmospheric pressure is compressed to 0.700 L at constant temperature. Calculate the final pressure of the gas

P2V2 P2 P2 P2

## = P1V1 = P1V1 V2 = (1 atm)(1.00 L) 0.700 L = 1.43 atm.

EXERCISES: A sample of oxygen gas occupied a volume of 42.5 cm3 at 25 oC and 1 atm pressure. What will be its volume when the pressure is increased to 1.8 atm, at constant temperature?

## P1V1 = P2V2 1.0 x 42.5 = 1.8 x V2 V2 = 23.6 cm3

EXERCISES: 250 cm3 of chlorine gas at 200 kPa is compressed, at constant temperature, until its pressure is 400 kPa. What is the final volume occupied by the sample of chlorine gas?

## = P2V2 400 x V2 = 125 cm3

EXERCISES: 9.97 dm3 of air at 119.0 kPa is allowed to expand, at constant temperature, to 12.0 dm3. calculate the final pressure.

= = =

## Charles law: the effect of temperature on the volume of a gas

* Charles law state that at constant pressure, the volume of a fixed mass of gas is directly proportional to its absolute temperature * Mathematically expressed as:

## * or it can be express in equation as:

V = k T V1 T1 V2 = T2

## * The volume-temperature relationship can be shown using the graph below:

EXERCISES: A sample of gas occupied a volume of 10.0 L at 50 oC. Assuming that the pressure remains constant, what temperature in oC is needed to reduce the volume to half?

## V2 T2 5.0 L = T2 5.0 X 323 10

EXERCISES: A sample of gas at 2.00 atm and 30 oC is heated at constant pressure to 50 oC. Its final volume is 5.0 L. what is its original volume?

V1 = T1 V1 (273 + 30) V1 V1

V2 T2 = = =

## 5.0 L (273 + 50) 5.0 X 303 323 4.7 L

EXERCISES: A sample of helium gas occupies 100 cm3 at 28 oC. At what temperature in oC will its volume be doubled under constant pressure?

V2 T2 = = = =

## 200 T2 273 + 28 100 602 K 329 oC

PRESSURE LAW

* Pressure law states that the pressure of a fixed mass of gas at constant volume varies directly with its absolute temperature. * This expressed mathematically as

P
* or it can be express in equation as:

P = k T P1 T1 P2 = T2

* EXAMPLE: * A fixed volume of gas at 30oC has a pressure of 101 kPa. If the pressure is increase to 113 kPa, calculate its temperature. SOLUTION:

P1 T1

P2 T2

## 101 = 113 (273 + 30) (273 + T2) T2 = 339 K

* Avogadros law states that all gases at the same temperature, pressure and volume contain the same number of particles. * This expressed mathematically as

## (At the constant pressure and temperature) Where n = number of moles

* the molar volume of a gas is the volume occupied by 1 mole of gas at standard temperature and pressure (s.t.p). This volume is 22.4 dm3 or 22400 cm3 * under room conditions, the volume is usually stated as 24.0 dm3

## The ideal gas law

* Using Boyles law and Charles law, it is possible to derive an equation relating all three functions of volume, temperature and pressure as follows

P1V1 T1

P2V2 T2 PV T
= a constant

## * This means that for a given mass of gas,

* For 1 mole of a gas, this becomes constant. And for n moles of gas,

## PV = R where R is the gas T nRT

PV

* Where: * R has a value of 8.314 J K-1 mol-1 in SI units if: * the pressure (P) is measured in pascals (Pa) * the volume (V) is measured in cubic metres (m3) * the temperature (T) is measured in Kelvin's (K) * R has a value of 0.082 dm3 atm k-1 if: * the pressure (P) is measured in atmospheres (atm) which is 1 atm = 101 kilopascals (kPa), while 101 x 103 Pa = 760 torr or 760 mm Hg * the volume (V) is measured in dm3 * the temperature (T) is measured in Kelvin's (K) * and n in moles (mol)

## DALTONS LAW OF PARTIAL PRESSURE

* Daltons law state that the total pressure of a mixture of gases equals the sum of the partial pressures of the gas present in the mixture. * PTOTAL = PA + PB + PC + * Where PTOTAL = Total pressure of the gas mixture PA, PB and PC respectively * While the partial pressure of gas is the pressure that a gas in a mixture would exert if it alone occupied the whole volume of the gas mixture at the same temperature.
The partial pressure (PA) of gas A Number of moles of A Total number of moles of gases in the mixture

PTOTAL

EXAMPLE

*A container of volume 2 dm3 contains 0.4 mol of oxygen and 1.2 mol of carbon dioxide under a total pressure of 100 kPa. Calculate the partial pressure of each gas in the mixture. *Answer Total number of moles of gas = 0.4 + 1.2 = 2.6 mol Mole fraction of oxygen = 0.4/1.6 = 0.25 Mole fraction of CO2 = 1.2/1.6 = 0.75 Partial pressure of oxygen = 0.25 x 100 kPa = 25 kPa Partial pressure of CO2 = 0.75 x 100 kPa = 75 kPa

Brain test

## TRY THIS QUESTIONS

* 2.5 dm3 container contains 0.1 mol nitrogen and 0.25 mol oxygen at 25 oC. Calculate the partial pressure of each gas and the total pressure of the mixture. *Answer Using pV = nRT For nitrogen: p X (2.5 X 10-3) = 0.1 x 8.31 x (25 + 273) p = 9.91 x 104 Pa For oxygen: p X (2.5 X 10-3) = 0.25 x 8.31 x (25 + 273) p = 2.48 x 105 Pa

Total pressure of the mixture = (9.91 x 104) + (2.48 x 105)Pa = 3.47 x 105 Pa

## TRY THIS QUESTIONS

* 100 cm3 of oxygen gas at 105 kPa is mixed with 200 cm3 of nitrogen gas at 300 kPa. What is the partial pressure of oxygen and nitrogen in the mixture assuming that the temperature remain constant. *Answer Using pV before mixing = pV after mixing Total volume after mixing = 100 + 200 = 300 cm3 Partial pressure of oxygen = (100/300) x 150 kPa = 50 kPa Partial pressure of nitrogen = (200/300) x 300 kPa = 200 kPa

## TRY THIS QUESTIONS

* 1.0 dm3 of gas A at a pressure of 505 kPa and 2.5 dm3 of gas B at a pressure of 232.3 kPa were forced into a container of 0.7 dm3 capacity. Calculate the total pressure in the 0.7 dm3 container. The temperature remain constant throughout. *Answer For gas A The volume was reduced from 1.0 dm3 to 0.7 dm3 under constant pressure. Using Boyles Law: p1V1 = p2v2 505 x 1 = p2 x 0.7 p2 = 721.4 kPa

## TRY THIS QUESTIONS

*Answer For gas B The volume was reduced from 2.5 dm3 to 0.7 dm3 Using Boyles Law 232.2 x 2.5 = PB x 0.7 PB = 829.3 kPa The total pressure = 721.4 + 829.3 The total pressure = 1550. 7 kPa

## DETERMINING RELATIVE MOLECULAR MASS

* The ideal gas equation can be used to determine the relative molecular mass of a substance. * PV = nRT and n = m/Mr * Where n = number of moles, m = mass of the sample, Mr = relative molecular mass * Thus, after making the modification, the equations below was produced: PV
= m RT

Mr

mRT Mr = PV

## Explaining deviations from ideality

*Ideal gas is the gas molecules that have no volume, and there are no intermolecular forces between the molecules. *However for real gases, the molecules have a volume and there are intermolecular forces between them *At high pressures, the volume occupied by the gas is small and the volume of the gas molecules cannot be ignored *The molecules are pushed so close together that a repulsive force operate between them making the gas less compressible *At low temperatures, the kinetic energy of the molecules is low. The intermolecular forces between the molecules become more apparent.

## Explaining deviations from ideality

*While real gases show a marked deviation from ideal behavior under high pressure and low temperature *All real gases behave almost ideally under very low pressure and very high temperature. *Low pressure = the volume occupied by the gas is very large, the volume of the gas molecules by comparison is extremely small and can be ignored *High temperatures = the kinetic energy of the molecules is so high that the intermolecular forces operating between them can be ignored

## Explaining deviations from ideality

*At room conditions (25 oC and 1 atm), the deviation of real gases from ideal behavior is about 3% *Small non-polar molecules such as hydrogen and helium show the least deviation, while big polar molecules such as ammonia and sulphur dioxide show a marked deviation from ideal behavior.

## Kinetic theory of liquids

* Liquid are intermediate in character between solids and gases. * Properties of solids, liquid and gases:

Solid

Liquid

Gas

Particles arranged fixed and very close Forces very strong Space between particles can be negligible

Particles arranged random and close Forces strong Space between particles is very small

Particles arranged random and far apart Forces very weak Space between particles is very big

Melting process

* in solids, the particles are very closely packed together in a fixed, orderly structure. *Strong intermolecular forces prevent free movement of the particles. *The particles can only rotate or vibrate in their position *When heated, the kinetic energy of the particles increases. *The extent of rotation and vibration increases. *A point is reached when the kinetic energy is high enough to overcome the intermolecular forces between them *The particles are liberated from their position and can now move more freely.

## Evaporation and condensation process

* The particles in a liquid are in constant motion, however, these particles do not possess the same kinetic energy. As a result of random collisions, some particles at the surfaces holding them within the liquid. The process in which liquid particles with sufficient energy escape from the liquid surface and enter the gas phase is called evaporation. * Evaporation occurs at the surface of a liquid at any temperature below the boiling point of the liquid. Since the particles which escape from the liquid during evaporation are the ones with the highest kinetic energies, the average kinetic energy of its remaining particles will fall. Consequently, the temperature of the liquid will fall as the liquid evaporates * The evaporation process occurs continuously.

## Evaporation process in the closed container

Vapour

Vaporisation

condensation

* When, the evaporation occurs, the particles in the vapour state will collide with the walls of the container. * Some of the particles while bouncing within the enclosed space, will hit the liquid surface and re enter the liquid phase. The change of state in which a vapour or a gas is changed into a liquid is called condensation.

Boiling of liquid

*If a liquid is heated in an open container, its saturated vapour pressure increases. *When the saturated vapour pressure becomes equal to atmospheric pressure, bubbles of vapour will form in the liquid and escape into the atmosphere because the vapour pressure is high enough to overcome the external pressure. *The saturated vapour pressure of water is equal to the external pressure (1 atm) at 100 oC. Hence water boils at 100 oC *Heat must be supplied continuously to sustain boiling. When a liquid boils, the heat supplied is used to break the intermolecular forces between the particles in the liquid and not used to increase their kinetic energy. The temperature will not change as long as there is liquid left

Boiling of liquid

*The boiling point of a liquid is the temperature at which its saturated vapour pressure is equal to the external pressure *The boiling point depends on the the external pressure. *Example: water boils at 100 oC under a pressure of 101 kPa, but boils at 14 oC under a pressure of 1.6 kPa *A volatile liquid is one with high saturated vapour pressure at any given temperature. *The intermolecular forces holding the particles in the liquid state are weak, therefore the particles have a higher tendency to escape as vapour. *The more volatile a liquid, the lower its boiling point.

FREEZING

*When the temperature of a liquid is lowered, the kinetic energy of the particles decreases *A point is reached when the intermolecular forces are strong enough to hold the particles together in a fixed, orderly arrangement. *The freezing point is the temperature where a solid is in equilibrium with its liquid under a pressure of 1 atm

## Solid : lattice structure

* most solid are crystalline. In crystalline solids, the particles are arranged in an orderly manner. *In solid, the particles are held rigidly together by strong attractive forces in a three dimensional structure called the lattice structure. *Solids are more dense than liquids *In amorphous solids, the particles are not arranged in an orderly manner *The basic repeating unit of a crystalline solid is called a unit cell

Unit cell

CRYSTAL STRUCTURE

* Crystal lattice regular arrangement of particles solid. *The unit cell is the smallest block of particles which when repeated throughout the crystal reproduce the crystal structure *There are 7 types of unit cells: *Cubic *Hexagonal *Tetragonal *Orthorhombic *Rhombohedral *Monoclinic *Triclinic

Cubic

*a=b=c * xo = yo = zo = 90 o * Example : Sodium chloride, barium flouride, potassium iodide, iron, copper

Hexagonal

*a=bc * xo = yo = 90o, zo = 120o * Example : scandium, aluminium chloride, iron (II) sulphide, phosphorus (V) oxide

Tetragonal

Orthohombic

## *abc * xo = yo = zo = 90o, * Example : sulphur. Lead (II) chloride, silver nitrate,

barium carbonate, calcium sulphate (V)

Rhombohedral

## *a=b=c * xo = yo = zo 90o, * Example : Bismuth, antimony, arsenic, calcium carbonate

Monoclinic

*abc * xo = zo = 90o yo 90o * Example : sulphur, magnesium chloride, calcium iodide (V), copper (II) fluoride

Triclinic

*abc * xo zo yo 90o * Example : copper (II) sulphate (VI), pentahydrate, bismuth nitrate, calcium carbide

## Cubic LATTICE SYSTEM

*There are 3 types of cubic lattices *Simple cubic *Body-centred cell *Face-centred cell

## Cubic LATTICE SYSTEM

*Simple cubic *In a simple cubic cell, the particles occupy the eight corners of the cube. *Example of solid with simple cubic is potassium chloride
Simple cubic

## Cubic LATTICE SYSTEM

*Body-Centred Cubic *In the body-centred cubic, the particles occupy the eight corners of the cube as well as the centre of the cube. *Example of body-centred cubic are sodium and caesium chloride.
Body-centered cubic

## Cubic LATTICE SYSTEM

*Face-Centred Cubic *In the face-centred cubic cell, the particles occupy the centre of each of the six faces in addition to the eight corners of the cube *Example of the face-centered cubic structure are sodium chloride and iodine Face-centered cubic

*A particle in a unit cell can be found in 4 different positions *In each position, it only contributes a fraction of its volume or mass to its unit cell. *The number of nearest equidistant particle in a crystal structure is termed its coordination number

## Particle in center of unit cell

allotropy

*Is the existence of different forms of the same element in the same physical state *Allotropes have different physical and chemical properties *The allotropes of carbon: *There are three allotropes of carbon *Graphite *Diamond *Fullerene

## Each carbon atom is sp2 hybridised, bond angle is 120o

The weak van der Waals forces between the layers enable them to slide over each other. Therefore, graphite is used as a lubricant
Uses: Lubricants and as electrodes in electrochemica l and electrolytic cells

The unhybridised p electrons form a delocalised cloud of electrons enabling graphite to conduct electricity and giving graphite its shiny appearance

Each carbon atom is covalently bonded to three other carbon atoms to form flat sheets of interconnecte d hexagons; weak nondirectional van der Waals forces attract the sheets or layers to each other

DIAMOND

All the valance electrons of the atoms are involved in bonding making diamond a nonconductor of electricity Each carbon atom is sp3 hybridised, bond angle is 109.5o Each carbon atom is covalently bonded to four other carbon atoms located at the corners of a tetrahedron, forming an interconnected network of 6membered ring

The 3-dimentional network of covalent bonds binds all the atoms into a giant molecular structure. Thus, diamond is a hard solid

## Density = 3.5 g cm-3

Uses : diamond-tipped tools are used for cutting and engraving. Diamond has a high refractive index making it a prizes jewel

fullerene

Also known as buckminsterfullerene with the formula C60 Other forms of fullerenes with the formulae C70, C76, C82 and C90 are also known The C60 fullerene, commonly known as Buckyball is spherical and consists of 60 carbon atoms It is made up 32 faces that is 12 pentagonal faces and 20 hexagonal faces Each carbon atom in the fullerene is sp2 hybridised Fullerene are used to make superconductors, lubricants, micro-ball bearings in nanomachines such as micro-motors and also as abrasives

## The allotropes of sulphur

There are 2 allotropes of sulphur Rhombic sulphur ( -sulphur ) Monoclinic sulphur ( -sulphur )

Rhombic sulphur

monoclinic sulphur

## THE CHARACTERISTIC OF THE 2 ALLOTROP

Formula S8 Octahedral shape Yellow transparent crystal Density = 2.06 g cm-3 Melting point = 113oC Stability : stable at temperature < 95.6oC at 1 atm Soluble in carbon disulphide, CS2

Formula S8 Needle shaped Yellow translucent crystal Density = 1.96 g cm-3 Melting point = 119oC Stability : stable at temperature > 95.6oC at 1 atm Insoluble in carbon disulphide, CS2

Phase diagrams
A phase diagram summarises the relationship between the solid, liquid and gaseous states of a given substance as a function of the pressure and temperature on a single graph Every substance has its own individual phase diagram. The phase diagram is a graph plotted from experimentally obtained results

Phase diagram of water Represents the vapour pressure of water below its freezing point At any point on this curve, water exists in a metastable condition since water dies not normally exist as a liquid below its freezing point The phenomenon represented by this curve is termed This line is the melting temperature curve. It shows supercooling the effect of pressure on the melting point of ice The curve slopes to the left with increasing pressure showing that as the pressure is increased, the melting point of ice decreases slightly. This is unusual because an increase in pressure usually favour the formation of solid. However, this Represents the ice having an open behaviour is due tovapour pressure- structure. As temperature curve for water the pressure is exerted is increased, the hydrogen bond between the H2O molecules in ice are Represents the sublimation vapourAlong this curve, liquid water and water broken vapour are equilibrium down, changing the ice into a denser liquid phase pressure-temperature curve for ice which occupies as the pressure (at It gives the conditions of pressure It shows that a smaller volume which and temperature at which ice andwater is held) is increased, its boiling point also increases water vapour are equilibrium

This is the melting point of ice of the freezing point of water at 1 atm At this point (0oC and 1 atm), water and ice are in equilibrium with each other

This is boiling point of water at 1 atm. The temperature is 100oC At this point (100oC and 1atm), both water and water vapour are in equilibrium with each other This is called critical point of water The critical temperature (Tc) is 327oC and critical pressure (Pc) is 220 atm Beyond the critical point, the liquid form water cannot be distinguished from its vapour form, that is there is no meniscus separating liquid water from water vapour. Also, beyond this point water vapour cannot be changed into liquid water no matter how much pressure is applied

This is known as the triple point where all the phases, ice (solid), water (liquid) and water vapour (gas) are equilibrium. This occurs at 0.01oC and 0.006 atm. Under these conditions, the vapour pressure of ice and water are the same

Example 1

## Phase diagram of carbon dioxide

The solid-liquid equilibrium line, OC slope to the right, as is typical of most substances. This indicates that the melting point of carbon dioxide increase in pressure. This is because solid carbon dioxide is denser than liquid carbon dioxide since the molecules in the solid state are more closely packed. According to Le Chateliers Principle, increasing pressure will shift the position of equilibrium towards the left hand side. Hence, it is more difficult to melt solid carbon dioxide at high pressure. The triple point occurs at 5.1 atm that is above 1.0 atm. Therefore, at all pressures below 5.1 atm, no liquid carbon dioxide can exist.

Its also indicates that the solid carbon dioxide will not melt but sublime at room condition If solid carbon dioxide is warmed at 1.0 atm, it sublimes at -78oC, passing directly from the solid phase into the gaseous phase without through the liquid phase. This phenomenon is used in industry to freeze foods like ice cream. Solid carbon dioxide or dry ice is used because it will not melt and will not wet the food To obtain liquid carbon dioxide, a pressure greater that 5.1 atm would have to be obtain

Uses of solid carbon dioxide (dry ice) solid carbon dioxide is used as a refrigerant for foodstuffs such as ice cream since it does not melt on warming It is also used in cloud seeding to encourage the formation of ice crystals in clouds. As the dry ice sublimes, it absorbs heat in the clouds, thereby lowering the temperature and causing the water vapour to condense and form water. Cloud seeding is carried out to induce rainfall especially after long period without rain

## Effect of non-volatile solute on water vapour press Lowering of vapour pressure

The vapour pressure exerted by a pure liquid is dependant only on the temperature and not the amount of liquid present as long as the liquid is in equilibrium with water When a non volatile solute is added to a pure liquid, the vapour pressure exerted by the solution is less than the vapour pressure exerted by the pure liquid at the same temperature.

This happens because part of the surface of the solution is occupied by solute particles (non volatile liquid), fewer solvent particles (pure liquid) can escape to form vapour. But the vapour particles still have the whole surface of the solution to return to the liquid, so there are less vapour pressure particles present at equilibrium, causing the vapour pressure to be lower The more concentrated the solution, the lower the vapour pressure of the solution

Refer to Pre U text book: Figure on page 67 Example 3.5 and 3.6 page 67

## Effect of non-volatile solute on water vapour press Colligative properties

is a properties which depends on the number of dissolve particles and not on the nature of the solute particles in the solution. The 4 common colligative properties are:
Elevation of the boiling point of a solution Depression of the freezing point of a solution Lowering of the vapour pressure of a solution Lowering of the osmotic pressure of a solution

when a non volatile solute (for example, sodium chloride or glucose) is dissolved in a solvent, the vapour pressure of the solvent is lowered. This is shown by line Q in the previous figure. As more solute is added, the solution becomes more concentrated and the vapour pressure is lowered even further (line R) This happen because solute molecules at the surface of the solution hinders the escape of the solvent molecules. However, the return of the solvent molecules from the vapour phase to the liquid phase is unaffected. The result is a reduction in the vapour pressure of the solvent. This can be se seen in the previous figure where Fr and Fq represent the freezing points of the dilute and concentrated solutions and Br and Bq represent the boiling points of the dilute and concentrated solution

## Depression of freezing point and the cryoscopy constant, K f

When a solute is dissolved in a solvent, it will cause a decrease in the freezing point of the solvent The equation relating this decrease in the freezing point to the concentration of the solution is given by:

Example

## Elevation of boiling point and the ebullioscopy constant K b

the elevation in boiling point caused by a solute dissolving in a solvent is given by:

Example

Finish Daa