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Chapter 1: Matter http://chemistry.about.com/od/chemistry101/a/atomstudyguide.htm 1.1 Basic particles in an atom 1. Protons, neutrons and electrons.

relative mass proton 1 neutron 1 electron 1/1836 1 a.m.u. (atomic mass unit) = 1.66 x 10-27 kg gold relative charge +1 0 -1

-particle

http://richardbowles.tripod.com/chemistry/structure/structure.htm 2. No of protons = ATOMIC NUMBER of the atom

The atomic number is also given the more descriptive name of proton number. No of protons + no of neutrons = MASS NUMBER of the atom The mass number is also called the nucleon number. This information can be given simply in the form:

3. Isotop Isotopes are atoms which have i) ii) The same atomic number but different mass numbers. They have the same number of protons but different numbers of neutrons. Same chemical properties

iii)

Different physical properties e.g. b.p./m.p./density

Stable isotopes (Z = 1 20, 21 -83) Unstable isotopes (Z = > 83), decay spontaneously

Examples of isotopic decay a) Alpha decay follows the form:

e.g. 23592U 23190Th + 42He2+ () Alpha decay is the most common in elements with an atomic number greater than 83.

b)

Beta negative decay follows the form:

e.g. 146C 147N + 0-1e() Beta decay is most common in elements with a high neutron to proton ratio. c) Gamma decay follows the form:

e.g. 156C 157N* + 0-1e


15 7

N+

38

16

S 3817Cl 3818Ar

1.2 Atomic Mass & Molecular Mass

1 unit of atomic mass = 1/12 (atomic mass C-12) =


1 (12/(6 x 1023) g 1 2

= 0.166 x 10-23 g = 1.66 x 10-24 g = 1.66 x 10-27 kg Relative atomic mass (Ar) = mass of an atom of an element 1/12 x mass of C-12 atom = mass of an atom of an element x 12 mass of 12C atom = mass of a molecule 1/12 x mass of C-12 atom = mass of a molecule x 12 Mass of 12C atom = mass of an atomic isotop 1/12 x mass of C-12 atom = mass of an atomic isotop x 12 mass of 12C atom = mass of 1 unit of ionic compound 1/12 x mass of C-12 atom = mass of 1 unit of ionic compound x 12 mass of 12C atom

Relative molecular mass (Mr)

Relative isotopic mass

Relative formula mass

Relative isotopic mass = m1a1 + m2a2 + . a1+ a2 +. e.g.

Mass Spectrometer

Accelerates the +ve ions (8000V)

Sample is injected as a gas

High ratio of m/e deflected less

Heated filament gives electrons

Ions with correct ratio of m/e

Recorder current operates a pen and trace a peak on recording

Amplifier charge received by the collector is turned into a sizeable current

1.3 How a spectrometer works (refer to CD 1) Atoms can be deflected by magnetic fields - provided the atom is first turned into an ion. Electrically charged particles are affected by a magnetic field although electrically neutral ones aren't. The sequence is : Stage 1: Ionisation The atom is ionised by knocking one or more electrons off to give a positive ion. Mass spectrometers always work with positive ions. Stage 2: Acceleration The ions are accelerated so that they all have the same kinetic energy. Stage 3: Deflection The ions are then deflected by a magnetic field according to their masses. The lighter they are, the more they are deflected. Different ions are deflected by the magnetic field by different amounts. The amount of deflection depends on: the mass of the ion. Lighter ions are deflected more than heavier ones. the charge on the ion. Ions with 2 (or more) positive charges are deflected more than ones with only 1 positive charge. These two factors are combined into the mass/charge ratio. Mass/charge ratio is given the symbol m/z (or sometimes m/e).

For example, if an ion had a mass of 28 and a charge of 1+, its mass/charge ratio would be 28. An ion with a mass of 56 and a charge of 2+ would also have a mass/charge ratio of 28. Stage 4: Detection The beam of ions passing through the machine is detected electrically.

Exercise(examples) http://www.algebralab.org/practice/practice.aspx?file=Algebra_AverageAtomicMass.xml 1.4 The Mole 1. Definition: 1 mole of an element the amount of an element that contains 6.022 x 1023 atoms(or the same number of atoms as 12 g of carbon -12) 12g C 24 g Mg 56 g Fe 40 g Ca All these masses contain the same number of atom i.e. 6.022 x 1023 2. Molarity - aqueous solutions - unit mol dm-3 - n = mv/1000 e.g. a) 10 g NaCl is dissolved in 100 cm3 water. Calculate the molarity of the solution. b) How many grams of copper sulphate is required to prepare a solution of 0.25 mol dm-3 in a 250 cm3 volumetric flask. You are given CuSO4.5H2O crystals. 108 g Ag

3. Molar Volume 1 mol of any gas = 22.4 dm3 at s.t.p.( 00C, 1 atm) = 24 dm3 at r.t. (250C, 1 atm)

Number of particles mass 6 x 1023 Ar/Mr MOL 22.4 dm3/24 dm3 Volume of gas Molarity

1.5 Physical States of Matter Gas - 3 physical states of matter gas, liquid & solid depending on conditions, temp & pressure. - Gasses differ from solids & liquids i) gases are highly compressible ii) gases expand on heating iii) gases flow much more freely than solids/liquids iv) gases have low densities 1.5.1 Boyles Law - for fixed mass of gas at constant temperature the product of pressure and volume is constant
P p pV pV

V 1/p V = k/p pV = k
V 1/v p v

http://www.grc.nasa.gov/WWW/K-12/airplane/boyle.html http://www.chem.iastate.edu/group/Greenbowe/sections/projectfolder/flashfiles/gaslaw/boyles_law_graph.ht ml

Examples 1. If some neon gas at 121 kPa were allowed to expand from 3.7 dm3 to 6.0 dm3 without changing the temperature, what pressure would the neon gas exert under these new conditions?

2. A quantity of gas under a pressure of 1.78 atm has a volume of 550 cm3. The pressure is increased to 2.50 atm, while the pressure remains constant. What is the new volume? 3. Under a pressure of 172 kPa, a gas has a volume of 564 cm3. The pressure is decreased, without changing the temperature, until the volume of the gas is equal to 8.00 x 102 cm3. What is the new pressure?
Ans wers: 1) 75 kPa 2) 390 cm3 3) 121 kPa

1.5.2 Charles Law - at constant pressure, the volume of gas increased in a linear manner with temp. V T V = kT V/T = k V1/T1 = V2/T2
V V

0K(-273.15oC) P

T(oC) V

T(K)

T2 T1 V T2> T1 P T P1 < P2 < P3 T(K)

1.5.3 Equation of State For an Ideal Gas

gases generally do not obey Boyles Law & Charles Law under all conditions real gases ideal gas a gas that obeys both laws PV = k1 (B) V/T = k2 (C) Combining both laws, PV/T = constant or
P1 1 V P 2V 2 = T1 T2

1.5.4 Avogadros Hipothesis equal volumes of gases measured at the same conditions of temp & pres., contain the same number of molecules. At s.t.p. (0oC, 1 atm) volume of any gas 22.4 dm3 1.5.5 The Ideal Gas Equation 1. For gases that obey the ideal gas equation PV/T = constant ( for a given mass of gas) PVm = RT ( Vm volume for 1 mole, R universal gas constant) Therefore, for n moles of gas, PV = nRT R = PV/nT = 1.0132 x 105 x = 8.314 JK-1mol-1 OR R=
(1atm )( 22 .4dm 3) = 0.082 atm dm3mol-1K-1 1( 273 K )

22 .44 3 1 m x 1000 273 .15 K

1.5.6 Daltons Law of Partial Pressures - in a mixture of gases which do not react chemically, the total pressure is the sum of the partial pressure of the components. PT = PA + PB + PC + Whereby PA, PB, PC are the partial pressures of gas A, B and C respectively. - the partial pressure of each gas depends on the total pressure and on the mole fraction of the gas. Mole fraction of A = molesofA + molesofB
molesofA

nA nA + nB

1.5.7 The Kinetic Theory of Gases According to the kinetic theory,

i) ii) iii) iv) v) vi) vii)

gas molecules themselves occupy only a tiny fraction of the volume in which a gas is contained. ( sample of a gas merely an empty space) molecules of gas are far apart scattered with large distances between them and the Van der Waals forces acting between molecules are very weak almost negligible. Gas molecules are in constant motion moving in straight lines till they collide with each other or the walls of the container. Collision are perfectly elastic bounce apart with no loss of energy. Molecules have a range of speeds. The speed of a molecule depends on its kinetic energy. Average kinetic energy (1/2 mv2) is proportional to the absolute temp. Absolute zero temp , K.E. , speed , until all molecules stop moving. K.E. 0 & the temp is called absolute zero (-273.15oC/ 0K)

http://www.chm.davidson.edu/ChemistryApplets/KineticMolecularTheory/BasicConcepts.html

area under the curve are all the same same number of molecules most molecules - v but some are higher or lower as temp , no. of molecules with higher energy but no of molecules with heat is supplied, K.E. .

1.5.8 Deviation from an Ideal Gas 1. Ideal Gas - assumption volume is negligible - no forces between molecules therefore for real gases to behave like ideal gases, best under conditions of - low pressure (< 5 atm) - high temp (> 273 K) cos at low pressure molecules are far apart, therefore volume at high temp K.E. of molecules , therefore forces between molecules are not effective 2. Non- ideal gas (real gas) changes to liquid at low temp and high pressure - volume is not negligible

- forces between molecules exist a) in case of high pressure molecules are very near to each other - volume occupied by the molecules must be accounted for - forces between the molecules quite strong b) in case of low temperature molecules with low K.E. - forces between molecules takes effect - distance between molecules smaller - volume occupied by molecules cannot be neglected 3. Comparing ideal gases and real gases i) effect of pressure on real gases ( temp constant isotermic pv
+ve deviation (due to volume of molecules) CH4 H2 NH3

-ve deviation (due to intermolecular Forces)

p Deviation of NH3 > CH4 > H2 - H2 smaller size, molecular volume , van der Waals forces between molecules , therefore less deviation - NH3 bigger size, molecular volume , van der Waals forces & molecules are polarized (hydrogen bonding) therefore more deviation. Ideal gas pV = RT 2 Real gas (p + a/v ) (v-b) = RT
Forces of attraction

when n = 1

volume not negligible

pV/RT

203 K(-70oC) 273 K (0oC)

1.0

Pressure(atm)

Nitrogen at various temperature a) deviation of gas becomes more obvious at lower temp., as temp , K.E. , molecular motion , therefore forces between molecules becomes more effective. b) Maximum deviation of gas occurs as temp approaches b.p. (gas liquid) at this temp, molecules are closer and the volume cannot be neglected.

1.5.9 Determination of Relative Molecular Mass pV = nRT pV =


m RT M r
m

Mr = pV RT = RT/p a) Direct Weighing

m/V =

- Fix tap 1 to a vacuum pump. Close tap2 - Empty the vessel and close tap 1. Weigh the vessel (m1)g. - Open tap 2. Fill the vessel with gas. Close tap 2. - Weigh the vessel with gas (m2) g. - Fill the vessel with water then weigh (m3)g. - Room temp = t oC pressure = 1 atm. (Calculation refer to Fajar Bakti pg. 41) b) Syringe Method (Mr volatile liquid) a weighted quantity of liquid is injected into a gas syringe, which is placed in an oven to vaporize the liquid. The volume occupied by the vapour is then measured. (calculation refer to Fajar Bakti pg.42)

Therefore, relative molecular mass, X = 106

1.6 Solids - most solids crystalline arranged in an orderly manner 3D struc lattice struc - basic repeating unit unit cell - amorphous particles not arranged in an orderly manner 1.6.1 Basic Crystalline System a) types of unit cell depends on length of its sides and angle between them 7 types of unit cells ( refer to CD) - cubic - hexagonal - monoclinic - orthorhombic c - tetragonal - triclinic b - rhombohedral a b) Simplest unit cell cubic system - 3 types of cubic system i) simple cubic system e.g. KCl number of particles/ unit cell - K+ = 4 x 1/8 = - Cl- = 4 x 1/8 = - No of K+Cl- pairs = - coordination no = 6 ii) body-centred cubic cell e.g. CsCl - Cs+ = 1 - Cl- = 8 x 1/8 = 1 - No of Cs+Cl- pairs = 1 - coordination no = 8 iii) face-centred cubic cell e.g. I2, Al - at the corners 8 x 1/8 = 1 - at the faces 6 x = 3 - total 4 particles - coordination no = 12 http://departments.kings.edu/chemlab/animation/nacl.html http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/Lecture1/Lec1.html#anchor2

octahedral

c) Number of particles in a unit cell e.g. i) unit cell of sodium chloride calculate the number of Na+ & Cl- ions in the unit cell distance between the pair of charged ion is 2.82 x 10-10 m. The volume occupied by one mole of sodium chloride is 26.99 cm3. Calculate the Avagadros constant number of Na+ Cl- pairs in 1 mole of NaCl. Ans:

d) Percentage of space occupied by atoms i) in a simple cubic structure no of particles at corners = 8 x 1/8 = 1 atom let atomic radius = r volume of sphere = 4/3 r3 = 4/3 (a/2)3 volume of unit cell = a3 % space = 4/3 (a/2)3 x 1/a3 x 100 = 52% a a

ii) body-centred cube cell - no of particles at corners = 8 x 1/8 = 1 - 1 in the centre - total no of particles = 2 - total volume occupied by sphere = 2 x 4/3 r3
2a 2

a a

a2 + 2a2 = (4r)2 3a2 = 16 r2 r2 =


3 2 a 1 6

a
2a 2

27 3 3 3 64 r = a 4 , therefore r = a 27 4 3 64 % space = 2 x 3 a
x

volume of cube = a3

a a
2a 2

100

a = 68%

iii) face-centred cubic cell - no of particles at corners = x 8 = 1 - no of particles at face = x 6 = 3 - total no of particles = 4 - total volume = 4 x 4/3 r3 1.6.3

a2 + a2 = (4r)2 2a2 = 16r2 a2 = 8r2 r2 = a2/8 22 a % space = 16/3 (22 a)3 x100 a3 = 74.05%

Allotropy - elements that exist in more than 1 form e.g. carbon graphite, diamond, fullerene (C60) http://www.saskschools.ca/curr_content/chem20/networks/allotrop.html

sulphur sulphur rhombic and monoclinic (S8) S(rhombic) >95.6oC S(monoclinic) <96.5oC S(rhombic)

1.7 Phase Equilibrium single component system system specific part of the universe that is separated for testing component the number of free chemical species that exist in a system phase part of a system that consists of homogenous (uniform) states. e.g. water & ice 2 phase & 1 component, oil & water 2 phases & 2 component 1. A particular phase is separated from another phase by a boundary it can differ physically or chemically water & ice H2O cemically the same A phase can be separated from another phase mechanically e.g. oil & water system Ice - water Oil water Steam water Ice water vapour Solid dissolved in water Ideal gas mixture Water and alcohol Sand and water phase 2 ( 1 solid & 1 liquid) 2 ( 2 liquid) 2 ( 1 liquid & 1 gas) 3 ( 1 solid, 1 liquid & 1 gas) 1 ( 1 liquid) 1 ( 1 gas) 1 ( 1 liquid) 2 ( 1 solid & 1 liquid)

1.7.1 Liquid 1. Kinetic Theory - Liquid state intermediate between the gaseous and solid states. - Arrangement of particles close, less dense than solids, constantly breaking down and reforming of structures. - Shape of liquid depends on container - Motion vibration, rotation and translation Gas liquid solid

low density easy to expand/compress fills container

high density hard to expand/compress takes shape of container

high density hard to expand/compress rigid shape

2. a) b) -

Equilibrium between solid, liquid and vapour Freezing ( liquid to solid) temperature decrease kinetic energy decreases intermolecular forces increases - fixed position when becomes solid freezing point temperature whereby solid and liquid exist in equilibrium

Vapourisation ( liquid to gas) temperature increases ( evaporation/ boiling) kinetic energy increases molecules vibrate and move faster until the kinetic energy is able to overcome the attractive forces between the molecules and escape into the air - rest of the molecules will have lower kinetic energy and therefore temperature falls - boiling point temperature whereby the liquid & gas co-exist in equilibrium and this temperature depends on pressure.

c) Vapour pressure (pressure due to free particles) http://www.chemguide.co.uk/physical/phaseeqia/vapourpress.html#top in a closed system vapourisation occurs as vapour pressure increases, rate of vaporization decreases till it reaches an equilibrium rate of vaporization = rate of condensation liquid vapour temperature vapour pressure volatile liquid v.p., b.p. b.p. temperature at which v.p. = external atmospheric pressure.

1.7.2 Phase Diagram of a Normal Substance a) Region of different phases

T triple point ( 3 phases in eq)(determines if a substance will sublime at atmospheric pressure) C critical point liquid and vapour are indistinguishable Line separating the solid phase and liquid phase slopes to the right ( as pressure , Le Chateliers Principle to remove the constraint it changes to liquid) b) Changing of phase at constant pressure

Fig 1

Fig 2

As the temperature increases to the point where it crosses the line, the solid will turn to liquid. In other words, it melts.(Fig 1) At a higher fixed pressure, (Fig 2) the melting temperature would be higher because the line between the solid and liquid areas slopes slightly forward.

According to Le Chateliers Principle, if the pressure is increased, the equilibrium will move in such a way as to counter the change you have just made. To make it melt at this higher pressure, you will have to increase the temperature a bit. Raising the pressure raises the melting point of most solids. That's why the melting point line slopes forward for most substances.

c) Changing of phase at constant temperature

(Compare this with that of water principle used in ice- skating) d) Critical point

Above the critical temperature, it is impossible to condense a gas into a liquid just by increasing the pressure. All you get is a highly compressed gas. The particles have too much energy for the intermolecular attractions to hold them together as a liquid. e) Normal m.p. and b.p.
Normal m.p. and b.p. are observe at 1 atm pres. If the triple point is at a pressure higher than 1 atm then the substance will sublime at room pres and temp. e.g. CO2

1.7.3 Phase Diagram of CO2

-57

In this phase diagram the triple point is well above atmospheric pressure. It is impossible to get any liquid carbon dioxide at pressures less than 5.11 atmospheres. That means that at 1 atmosphere pressure, carbon dioxide will sublime at a temperature of -78C. This is the reason that solid carbon dioxide is often known as "dry ice". You can't get liquid carbon dioxide under normal conditions - only the solid or the vapour. (Uses of dry ice cooling agt, cloud seeding, stage shows)

1.7.4 Phase diagram of Water

i) Notice the melting curve slopes to the left. Hence increasing pressure will cause the solid to occupy a smaller volume that is the liquid phase and hence ice melts when pressure is increased.

1.7.5 Physical Properties of Liquids a) Vapour Pressure - as temperature , v.p. b) Rate of evaporation , v.p. c) Boiling point - temp at which its v.p. is equal to the external pressure above it., therefore more volatile b.p. vapour pressure 1.0 atm A B C

TA A most volatile C b.p. highest

TB

TC

temp

1.7.6 Phase Diagram of 2-Component System (Colligative Properties of Solutions) - vap pres of solution < vap pres of pure solvent - surface of solution covered by solutes - as vap. pres solution needs higher temperature before vap pres reaches atm pres, hence b.p. . v.p.
pure solvent solution

1 atm

b.p.of pure solvent

b.p. of solution

temp

The Vapor Pressure of a Solution is Lower than that of the Pure Solvent