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MATTER

anything that occupies space and has mass. made up of particles (atoms, ions, molecules) atoms consist of a nucleus (protons and neutrons) surrounded by electrons.

Comparison of electrons, protons and neutrons Subatom Symbol Relative charge Relative mass In electric field In magnetic field Proton p +1 1 a.m.u. Deflected to negative plate Slight deflection because heavier Neutron n 0 1 a.m.u. Not deflected No deflection Electron e -1 1/1840 a.m.u. Deflected to positive plate Deflected more and the opposite direction of proton

Proton Number, Nucleon Number and Isotopes


Proton number = (Z) Nucleon number = (A) Symbol of an atom no. of protons in the nucleus of an atom the sum of the number of protons and neutron in the nucleus of an atom = Az Y

Isotopes = atoms of the same element that have the same proton number but different nucleon number.

Isotopes 1. Most elements exist as isotopes. Eg : 35Cl and 37Cl 2. So, the mass of element depends on the relative abundance of all the isotopes. Eg: 35Cl and 37Cl have a relative abundance of 75.8% and 24.2 % respectively. Relative atomic mass = 75.8/100 x 35 + 24.2/100 x 37 = 35.484 ~ 35.5 3. In an element, there are stable and unstable isotopes. Eg: 12C and 13C are stable but 14C is not stable

Relative Atomic Mass


Relative atomic = mass of one atom (element) Mass Ar 1/12 x mass of one atom of12C Relative molecular = mass of one molecule Mass, Mr 1/12 x mass of one atom of12C To calculate relative molecular mass, - Masses of isotopes and relative abundance must be known. - Values found using the Mass Spectrometer

Mass Spectrometer
Five main steps 1.Vapourisation If a sample is liquid or solid, it should be heated to form a gas. 2.Ionisation In the ionisation chamber, an electron gun produces a beam of high-energy electrons. highWhen hit by the electron beam, an atom in the chamber can lose an electron and form a positive ion. M (g) + eeM+ (g) + 2 e-

3. Acceleration Uses an electric field (plate P1 and P2 ) to accelerate the positive ions to speed. 4. Deflection The stream of fast moving ions is deflected sideways as it passes thru a magnetic field. The deflection of an ion depends on the charge of the ions and their mass Lighter ions deflected more than heavier ions.

5. Detection Ions of the same charge and mass will all follow one particular path. This stream of ions is detected by an instrument (electrometer) The path of a given ion depends on its mass, m and charge, e-, and specifically on its m/e eratio. The energy of the electron gun is usually set to form only ions with a charge of 1+ (unipositive ions).

Example of a spectrum from the spectrometer


X%

Relative abundance

Y%

Z%

m/e

Ar = X x a + Y x b 100 100

+ Z x c 100

The mole concept and calculations


1. Mole is the amount of any substance that
contains the same no. of particles as there are atoms in exactly 12g of C-12. C2. The no. of atoms = NA (Avogadro Constant) = 6.02 x 1023 3. The mass of one mole of atoms = molar mass, M . Unit = g mol-1 4. Amount of moles = mass of the sample (m) in a substance (n) Molar mass (M)

5. Solution Amount of moles = concentration of the solution solution x volume n = MV 1000 6. Gases n = volume of a gas molar volume 7. Dilution M1 V 1 = M2 V 2 (solute before dilution)= (solute after dilution)

States of Matter : GASES


GAS LAWS

A) Boyle s Law
1.

Pressure Volume Relationship Boyle noticed that when temperature is held constant, the volume (V) of a given amount of a gas decreases as the total applied pressure is increased. (atmospheric pressure plus the pressure due to the mercury added)

Boyle s Law states that : the pressure of a fixed amount of gas maintained at constant temperature is inversely proportional to the volume of the gas.

3. Mathematical expression will be : P 1/V So, P = k1 x 1/V k1 is a constant called proportionality constant 4. So, PV = k1 the product of pressure and volume is a constant for a gas at constant temperature (T) and amount of gas.(n) 5. So, k1 = nRT .

6. Graphs
P

0.6atm

0.3atm

2L

4L

P Gradient = k

1/V

PV

For a given sample of gas, at constant temperature and constant amount of gas, PV = constant Therefore, for a given sample of gas under 2 different sets of conditions at constant temperature , t P1V1 = k1 = P2V2 P1V1 = P2V2

Eg : An inflated balloon had a volume of 0.55 litres at sea level ( 1 atm) and is allowed to rise to a height of 6.5 km, where the pressure is about 0.4 atm. Assuming that the temperature remains constant, what is the final volume of the balloon? Solution Initial condition P1 = 1 atm V1 = 0.55 litres Final condition P2 = 0.4 atm V1 = ? P1V1 = P2V2 V2 = P1V1 = 1 x 0.55 = 1.4 litre P2 0.4

B. Charles Law 1. Charles law states that the volume of a fixed amount of gas maintained at constant pressure is directly proportional to the absolute temperature of the gas. gas. 2. So, V T V = k2 T or V/T = k2 k2 = nR P

An interesting phenomenon observed is that at any given temperature, the plot of volume against temperature yields a straight line.
V

-200

-100

100

200 T (0C)

By extending the line to zero volume, the intercept on the temperature axis is 273.150 C . For all different pressures, the line intercepts at the same point on the x (temperature) axis. Lord Kelvin identified -273.150 C as ABSOLUTE ZERO = theoretically the lowest attainable temperature. The absolute temperature scale is called the KELVIN TEMPERATURE SCALE

KELVIN TEMPERATURE SCALE


Kelvin Scale Celsius Scale

Absolute zero Freezing point of water Boiling point of water

0K 273.15 K 373.15 K

-273.17o C 00 C 1000 C

Under 2 sets of volume temperature conditions for a given sample of gas, V 1 = k2 = V 2 T1 T2 Considering the 2 laws together, ( Boyle s law & Charles law) The volume of a gas is dependent on the temperature and pressure as shown in the graph below

High temperature

volume

Low temp.

1/P

C. Avogadro s Law- volume-amount relationship


States that, at constant pressure and temperature, the volume of a gas is directly proportional to the number of moles of the gas present. So, V n V = k3 n The molar volume at STP (standard temperature and pressure) = 22.4 dm3 STP = (T = 0oC (273K), P = 1 atm /101.3kNm-2)

Ideal Gas Equation


Combining all 3 laws, n T or PV = nRT P R = the proportionality constant / gas constant. An ideal gas is a hypothetical gas whose pressure-volume-temperature relationship or behaviour can be completely accounted for by the ideal gas equation. V

Ideal Gas -The molecules do not attract or repel one another - their volume is negligible compared with the volume of the container Many real gases behave ideally under standard conditions (at STP)

Value of R R = PV nT Or

= (1 atm)(22.414 L) (1 mole)(273.15K) = 0.082057 L. atm /K . Mole = 8.31 Nm K-1 mol-1 = 8.31 J K-1 mol-1

Under 2 sets of conditions,

P1V1= P2V2 n1T1 n2T2

Measurement of Relative Molecular Mass Using Ideal Gas Equation


PV = nRT n =P V RT n = number of moles of the gas = m / Mr (m = mass in grams, Mr =
So, m Mr V molar mass) = P RT

Mr = m RT VP m /V is mass per unit volume which is density, d Mr = d RT P Example : A chemist synthesized a greenish yellow gaseous compound of chlorine and oxygen and found that its density is 7.71 g /litre at 360C and 2.88 atm. Calculate the molar mass.

Dalton s Law of Partial Pressures


Dalton s law states that : the total pressure of a mixture of gases is just the sum of the pressure that each gas would exert if it were present alone. Consider 2 gases, A and B, in a container of volume V. P A = nART PB = nBRT V V

Total pressure, PT = PA + PB = nART + nBRT V V = RT (nA + nB ) V = nRT (n = nA + nB) V Total pressure of a mixture of gases, PT = P 1 + P 2 + P 3 + (P1 , P2 , P3 are partial pressures of the component gases 1, 2 , 3 .)

PA = nA RT V Now, divide the equation with PT, PA PT = nA RT / V (nA + nB ) RT / V = nA / (nA + nB ) = XA ( mole fraction of gas A) = XA PT likewise , PB = XB PT

So, PA

XA + X B = 1

Example : A mixture of gases contain 4.46 moles of neon, 0.74 moles of argon and 2.15 moles of xenon. Calculate the partial pressures of gases if the total pressure is 2.0 atm at a certain temperature. XNe = 4.46 / 4.46 + 0.74 + 2.15 = 4.46 / 7.35 = 0.607 XAr = 0.74 / 7.34 = 0.100 XXe = 2.15 / 7.35 = 0.293 So, PNe = 0.607 x 2.0 = 1.21 atm Par = 0.100 x 2.0 = 0.20 atm PXe = 0.293 x 2.0 = 0.586 atm

Kinetic Theory of Gases


1.Gas laws help predict the behaviour of gases but do not explain what happens at the molecular level to cause the change we observe. 2. Ludwig Boltzmann & James Clark Maxwell - found that physical properties of gases can be explained in terms of the motion of individual molecules. - a number of generalisations about gas behaviour known as THE KINETIC MOLECULAR THEORY OF GASES

Kinetic Theory - Assumptions


1. A gas is composed of molecules that are separated from
each other by a distance greater than their own dimensions. Gases possess mass but have negligible volume. Gas molecules are in constant motion in random directions and they frequently collide with each other. Gas molecules exert neither attractive or repulsive forces on one another. Collisions are perfectly elastic total energy of all molecules in a system remain the same. Average kinetic energy of the particles is proportional to the absolute temperature. Gas pressure is caused by collision of molecules with the walls of the container.

2. 3. 4. 5. 6.

Kinetic Theory Laws

Application to Gas

Boyle s Law Pressure is the result of the collision on the walls of the container. Collision rate is proportional to the number density (number of molecules per unit volume). So, decreasing the volume, increases the number density, hence collision rate. Pressure increases.

Charles Law

V and T

Average kinetic energy of gas molecules is proportional to the absolute temperature. Raising the temperature increases average kinetic energy, molecules will collide with the walls more frequently, so pressure increases. So, volume will expand until the gas pressure is balanced by the constant external pressure.

Dalton s Law If molecules do not attract or repel each other, then pressure exerted by one type of molecule is unaffected by the presence of another gas. So, the total pressure is given by the sum of the individual gas pressures.

Distribution of Molecular Speeds


If temperature is constant, the average kinetic energy and the mean square speed will remain unchanged. Speed of a gas molecule is calculated as crms = 3RT/M (root mean square speed) Smaller the molecule, faster it moves. Maxwell analysed the behaviour of gas molecules at different temperatures and showed that different possible speeds are distributed among particles in a definite way.

Distribution of Speeds for Nitrogen Gas


100K Fraction of molecules 300K N2 (28.02g /mol)

700K

500

1000

1500 Molecular speeds m/s

At higher temperatures, more molecules are moving faster. The speed spread over a wider range.

Number of molecules

Ci2 (70.90g/mol)

T = 300K

N2 (28.02g/mol)

He (4.003g / mol)

500

1000

1500

2000

Molecular speeds m/s At a given temperature, lighter molecules arer moving faster on the average.

Maxwell Boltzmann Distribution


T1 No. of molecules Peak = most probable speed ( speed of the largest no. of molecules) T2 T2 > T1

Area = No. of molecules with speed c at T2

c As temp. increases, the peak shift to the right. The area below the 2 curves are the same Molecular speed m/s

Deviations from Ideal Behaviour


Real gases are not ideal. Why? Without intermolecular forces, gases cannot condense into liquid. Conditions for ideal gases - No intermolecular forces & gases have negligible volume BUT Real gases - Have volume and intermolecular forces, so they deviate from ideal behaviour

Real gases deviate from the equation PV = nRT at high pressures and low temperatures. Deviation can be shown using the graph PV/RT plotted against P. For an ideal gas, for 1 mole of gas, product of PV/RT = 1 regardless of the actual pressure. So, the graph is a straight line as shown.

PV/RT > 1 = positive deviation At 273K PV RT H2 CO2 O2

1.0 PV/RT < 1 = negative deviation

Pressure atm

Nitrogen gas at different temperatures PV RT

203K 273K 573K

1.0

Pressure (atm)

Deviation is dependent on -temperature, gases deviate at lower temperatures -pressure = gases deviate at higher pressures -Attractive forces between molecules

At low pressures (< atmospheric pressure), and high temperatures, all gases obey gas laws. Negative Deviation - occurs at low pressures. - Molecules are far apart, repulsive forces can be neglected. - Deviation is due to attractive intermolecular forces. This causes molecules to be closer, colliding less with the wall, so, measured pressure is less than the expected pressure. PV/RT < 1

Positive Deviation - Occurs at high pressures - Molecules are closer - Deviation is caused by repulsive forces - Gases collide with the wall, pressure increases - Measures pressure is higher than expected pressure - PV/RT > 1

Van der Waals Equation Van der Waals suggested that the pressure exerted by an ideal gas is related to the experimentally measured pressure, by the equation: (P + n2a ) (V n b ) =n RT V2 (corrected pressure) (corrected volume) (a and b are constants for different gases)

LIQUID
Kinetic Concept of the Liquid State In a liquid: - atoms or molecules are separated by greater distances than a solid. - Particles move slowly and randomly - Movement of these particles gives a liquid ability to flow, assuming shape of the container.

STATE / PHASE CHANGES


Temp. (K) Liquid & gas (boiling) Liquid Gas

Tb

Tm Solid

Solid & liquid (melting)

Time

Melting When a solid is heated, particles vibrate more vigorously. As temperature increases, the solid changes to a liquid at melting point. Melting point = the temperature at which the solid and liquid exist in a dynamic equilibrium At this point, the particles have enough energy to overcome / weaken the attractive forces within the solid. The energy absorbed is the latent heat of fusion. Freezing Substance changes from a liquid to a solid. Freezing point = temperature at which the liquid and the solid exist in dynamic equilibrium

Boiling Substance changes from liquid to gas. When a liquid is heated, there is a particular temperature at which vaporization occurs thru out the liquid. Vapor bubbles form within the liquid, rise to the surface and escape. When pressure exerted by the escaping molecules is equal to the external pressure, boiling occurs. Boiling point = temperature at which the vapor pressure of the liquid is equal to the standard atmospheric pressure (1 atm).

Vapourization / Evaporation - Substance changes from a liquid state to a gaseous state without heating. - Occurs below boiling point. - Molecules in the liquid state are in constant motion, occasionally, some molecules have enough kinetic energy to escape from the liquid surface and become vapour.

Factors that affect Vaporization 1. Temperature increase in temp., rate of vaporization increases. ( More molecules have sufficient kinetic energy to become vapor) 2. Surface area of the liquid. Increased surface area, more molecules escape into vapor. 3. External pressure. Decreased external pressure, more molecules escape into vapor.

In a Closed container, - Vapor molecules are trapped inside. - Eventually, the air above the liquid is saturated. - Vapor molecules occasionally strike the liquid s surface and return to the liquid state. - This process is condensation. - When the rate of evaporation and rate of condensation is equal, system is in dynamic equilibrium.

VAPOR PRESSURE Definition : The pressure exerted by vapor in dynamic equilibrium with its liquid. Liquids with high vapor pressure volatile. Volatility is dependent on the strength of the intermolecular forces. Weaker the forces more volatile the liquid. Eg: acetone, ether

Graph of Vapor Pressure against Temp.


Pressure, mm Hg
760

c a b

d a = diethyl ether b= benzene c=water d = toluene e e = aniline

34.6

80.1

100

Temperature, 0C

SOLID
Solids can be classified as : a. Crystals = particles arranged in 3 dimensions (salt, metal) b. Amorfus = no proper arrangement. (plastic, rubber etc) Structure of Crystals Lattice 3 dimensional patterns or structure (consist of 3 sets of parallel planes) Unit Cell Smallest structural unit which when repeated in 3 dimensions generates a crystal.

Unit Cells 7 types cubic, tetragonal, orthorhombic, hexagonal, rhombohedral, monoclinic and triclinic ( Refer to CD) Cubic Unit Cell 3 types simple cubic - body centred cubic - face centred cubic

Coordination Number = is the number of atoms with which a given atom is in contact with in a crystal lattice. No of atoms in a unit cell 3 types of lattice points a. Points positioned at the corners b. Points at the face c. Points inside the cell

Types of lattice points Corners Face centred Body centred Sides

Contribution to one unit cell 1/8 1 1/4

ALLOTROPES
Allotrope is the existence of two or more forms of an element that differ in their bonding and molecular structure. Eg : carbon 3 types diamond, graphite, fullerenes sulphur 5 types but 2 are common rhombic, monoclinic

PHASE DIAGRAMS
A phase diagram is a graphical way to summarise conditions under which equilibrium exist between different states of matter. Under appropriate conditions of temperature and pressure, a solid can be in equilibrium with its liquid state or with its vapor state.

General Form of a Phase Diagram D B Critical point

Pressure kPa

Solid

liquid

A Triple point Gas

Temperature / 0C

vapor pressure curve of the liquid vapor pressure curve of the solid change in melting point of the solid with pressure Point A = triple point . All three phases exist in equilibrium at this temp. and pressure. Point B = critical point. Highest temperature at which a substance can exist as a liquid. Beyond this point, the liquid and gas phases become indistinguishable. Line AB Line AC Line AD

Phase diagram of water and CO2 Refer to CD