Mass No Sub-atomic Relative Relative E = hf Energy = Plancks constant x frequency E(element) Atomic No particle charge mass Atomic number

Proton number Mass number Proton number plus the number of neutrons in the Proton +1 1 nucleus of its atom Electron -1 negligible Neutron 0 1 Hydration Chemical combination of water and another substance Solvent Substance in which other substances are dissolved Solute Substance dissolved in another substance(solvent)to form a solution Empirical formula Ratio of atoms of different elements present in a molecule of a compound, in their lowest terms as whole numbers (C4H4 has CH empirical formula) Molecular formula Actual number of atoms of each element in a molecule of a compound Dibasic acid One which has 2 replaceable H atoms per molecule Isotopes Atoms having the same atomic number but different mass numbers - As the number of protons increases, the number of neutrons increases relatively faster, so small atoms have proton and neutron numbers which are comparable whereas large atoms have more neutrons than protons - Neutrons reduce repulsive forces between positive protons - Departure from optimum range of ratio of protons to neutrons will lead to nuclear instability(radioactivity) - No of electrons in outer(valence)shell(and sometimes the shell next to the outer shell)and the IEs & EAs for an atom will determine the chemistry of the element - Outer shell electrons determine the chemistry of an element as they can get close to the outer shell electrons of other atoms, so can be transferred or shared. The inner shell electrons are tightly held and shielded from the electrons in other atoms/molecules - Isotopes dont affect the electron number or structure so dont affect the chemistry of the element, but have varying rates of reaction - 12C is the only atom with relative atomic mass which is an exact whole number because 12C is chosen as a standard and given a relative atomic mass of exactly 12 Nuclide A nuclear species of given mass number and atomic number Radionuclide Radioactive nuclide Relative atomic mass Average mass of an atom of an element compared with 1/12 of the mass of an atom of carbon-12 isotope Relative isotopic mass Mass of an atom of an isotope of an element compared with 1/12 of the mass of an atom of carbon-12 isotope Relative molecular mass Sum of relative atomic masses 1 Electrons are emitted from the filament, accelerated and used to bombard the gaseous sample which is at very low pressure 2 Sample molecules have electrons knocked off them by bombarding electrons forming positive ions. The molecules can also fragment or rearrange giving differen positive ions 3 Positive ions accelerated by an electric field 4 Positive ions deflected by a magnetic field in a circular path whose radius depends on mass/charge ratio and strength of the field. The machine sweeps over the chosen mass range by altering the magnetic field and hence ions reaching the detector are separated according to their mass 5 Positive ions(Species: radical cation/molecular ion/fragment ion) detected and relative amounts calculated by the machine - Chamber vacuumed to prevent air molecules obstructing the passage of particles through the mass spectrometer - Likelihood of 2+ ions being produced in the mass spectrometer is small, because the chance of a molecule being ionised by electron impact is already quite small. When it has been ionised it is pulled away by the potential gradient leading to the magnet which also hel to reduce the possibility of a second impact - Important to use minimum possible energy to ionise a sample in a mass spectrometer to prevent formation of double positive ions rath than single positive ions(or to prevent fragmentation of molecular substances)

(%Abundance x Mass) + (%Abundance x Mass) +.. Total % composition = Relative atomic mass RAM Molecular ion peak (The molecular ion peak is not always the most intense and maybe absent) Highest significant peak where the molecule has lost 1 electron but has not broken up Base peak Highest peak in the mass spectrum - If the sample is an element each line represents an isotope of the element - Molecules broken up into fragments make fragmentation patterns on the mass spectrum(used to identify molecules and structure) - Relative masses are just numbers, no units - No element in the periodic table has a relative atomic mass that is a whole number because relative atomic mass is an average so its not usually a whole number - Mass spectrometer with gas-liquid chromatography used in forensic work for analysis of complex mixtures, samples introduced to ga liquid chromatograph and various constituents separated, output gases then led to mass spectrometer, fragmentation patterns compared with large database of patterns from known substances - Once the electron has passed the final anode, it doesnt decelerate and go back to the anode because it has either collided with a gaseo molecule or passed on to earth(ground)at the other end of the chamber - It is a good approx to consider that relative atomic mass of 6Li+ determined in a mass spectrometer is the same as that of 6Li because mass of the electron lost from 6Li to form 6Li+ is negligible (1) Calculate RAM from these isotopes and their % compositions 54Fe 5.8%, 56Fe 91.6%, 57Fe 2.2%, 58Fe 0.33% (1) (54x5.8) + (56x91.6) + (57x2.2) + (58x0.33) 5.8 + 91.6 + 2.2 + 0.33 = 55.91(2dp) 1st Ionisation energy M(g) M+(g) + e Energy/enthalpy change per mole to remove an electron from each atom in the gas phase to form a singly positive ion 2nd Ionisation energy Energy/enthalpy change per mole for the process, M+(g) M2+(g) + e 1st Electron affinity X(g) + e X(g) Energy/enthalpy change per mole for each atom in the gas phase to gain an electron to form a singly negative ion - Negative(exothermic), since the electron is attracted by the positive charge on the atoms nucleus 2nd Electron affinity Energy/enthalpy change per mole for the process, X(g) + e X2(g) - Positive(endothermic), since energy needed to overcome repulsion between the electron and negative ions

Energy level Electrons in atoms can only have certain amounts of energy, groups of electrons can exist with roughly the same amount energy, these positions of roughly similar amounts of energy are called energy levels Size of IE depends on Nuclear charge Atomic radius Electron shielding, energy level Successive IEs increase because electrons are being removed from increasingly positive ions and so the attractive forces are greater - Large jumps in IEs arise from a large increase in attraction, corresponding to an electron being removed from a new energy level significantly closer to the nucleus(proving that electrons are arranged in shells) IEs increase across periods(left to right) Number of protons increasing, meaning stronger nuclear attraction Extra electrons are at roughly the same energy level, even if the outer electrons are in different orbital types Little extra shielding effect, little extra distance to lessen the attraction from the nucleus IEs decrease down groups Each element down a group has an extra electron shell Extra inner shells means extra distance of outer electrons from the nucleus, and greater shielding from the attraction of the nucleus, overall reducing nuclear attraction Atomic radius decreases across period 3(left to right) Nuclear charge increases, electrons pulled closer to the nucleus, electrons are a added to the same outer shell

n Subshell Number of electrons

Subshell Max number of electrons

1s 2

2s 2

2p 6

3s 2

3p 6

3d 10

4s 2

4p 6

4d 10

4f 14

Principal quantum number(n) shell numbers Subshell 1st shell has no subshell Orbital s subshell has 1 orbital, p has 3, d has 5 Aufbau build up principle Electrons are added to the lowest energy orbital available One at a time With no more than 2 electrons occupying one orbital If there are several orbitals of the same energy available then electrons enter these orbitals singly so as to be as far apart as possible Halogens have high IEs so they dont form positive ions but negative ions because they have one electron less than a full shell Anomalously low EA for F due to repulsion of the incoming electron from a concentrated electric field of a small atom

Quantum mechanics The electron in an atom behaves as a wave which is a mathematical construction, not a particle Atomic orbital IS the electron/pair of electrons, the volume in which the electron has a 95% probability of being found(no such thing an empty orbital) Spin is a property of an electron. The 2 electrons in an orbital have opposite spins, helping to counteract the repulsion between their negative charges(spin pairing)

Z Sy m bo l 1 2 3 4 5 6 7 8 9 10 11 12 13 14

1s

2s

2p

3s

3p

3d

4s

4p

H He Li Be B C N O F Ne Na Mg Al Si

1 2 2 2 2 2 2 2 2 2 2 2 2 2

Group II Group III Group V Group VI N 2s 2p

Be B N O

1s22s2 1s22s22px1 1s22s22px12py12pz1 1s22s22px22py12pz1 O 2s

1st IE = 900 kJmol1 1st IE = 799 kJmol1 1st IE = 1400 kJmol1 1st IE = 1310 kJmol1 2p

1 2 2 2 2 2 2 2 2 2 2 2

1 2 3 4 5 6 6 6 6 6

1 2 2 2

1 2

In B the 2p electron easier to remove than the 2s electron from Be because subshells that are full are more stable In B the 2p orbital is further from the nucleus The 2p orbital is screened not only by the 1s2 electrons but also partially by the 2s2 electrons - These factors are strong enough to override the effect of the increased nuclear charge resulting in the IE to drop slightly Screening identical and electron being removed is from an identical orbital N structure is symmetrical and more stable than that in O Repulsion between 2 electrons in the same orbital means an electron in the 2px2 pair is easier to remove

15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

P S Cl Ar K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As E Br Kr

2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2

2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2

6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6

(q) An atom contains 5 protons and 5 neutrons, give the symbol fo 2 3 this atom including the mass number (a) B 2 4 (q) Formula of the compound formed between this element and 2 5 chlorine (a) BCl3 2 6 2 6 1 2 6 2 2 6 1 2 2 6 2 2 2 6 3 2 2 6 5 1 2 6 5 2 2 6 6 2 2 6 7 2 2 6 8 2 2 6 10 1 2 6 10 2 2 6 10 2 1 2 6 10 2 2 2 6 10 2 3 2 6 10 2 4 2 6 10 2 5 2 6 10 2 6 (1)(i)Mass spectrum of HCl, peak at mass 36 is molecular ion (H 35Cl)+ Chlorine has only 2 isotopes 35Cl, 37Cl What particle is responsible for peak mass 38? (1)(i) (H 37Cl)+ (ii)How do you explain the fact that the height of the peaks at mass 36 is 3 times as high than the peak at mass 38 (ii)There is 3 times as much 35Cl to 37Cl and therefore 3 times as much H35Cl to H37Cl (2)(a)Mass spectrum of methane, peak at mass 16 is molecular ion(CH)+ Explain peaks of relative mass 1, 2, 12, 13, 14, 15, 17 Relative mass 1 2 12 13 14 15 17 (1H)+ (2H)+ (12C)+ (12C1H)+ (12C1H2)+ (12C1H3)+ (12C1H32H)+

(2)(a)Bromine consists of 2 isotopes, mass numbers 79 and 81. A sample of Br2(g) was examined in a mass spectrometer. Identify the species responsible for the peak at m/e = 160 (2)( 79Br81Br)+ (2)(b)For a particular sample of copper two peaks were obtained in the mass Peak at m/e Relative abundance spectrum 63 69.1 (i)Give the formula of the species responsible for the peak at m/e = 65 65 30.9 (i)65Cu+ (ii)State why two peaks, at m/e values of 63 and 65, were obtained in the mass spectrum (ii)2 different isotopes (3)How would accelerating field and magnetic field differ in its affect on X+ and X2+ ? (3)The accelerating force and deflecting field on X+ will be twice that on X+ (4)2 reasons why particles must be ionised before being analysed in a mass spectrometer? (4)Have to be accelerated, then deflected (5)Boron, relative atomic mass 10.8 gives 2 peak mass spectrum, m/z=10 and m/z=11 Calculate the ratio of the heights of the 2 peaks (5)10x + 11(1 x) = 10.8, x = 0.2, y =1 x = 0.8 ratio of heights = 1:4 (7)Explain why K has lower 1st IE than Na (7) Electron being removed is further from the nucleus More shielding Reduces attraction of the nucleus

6 (8)What force causes the scattering of particles by nuclei? (8) particles and nuclei both positively charged thus electrostatic forces of repulsion 5 (9)Explain why all isotopes of Mg have the same chemical properties (9) Same number of electrons in all Mg isotopes Outer electron structure 4 determines chemical properties + (10)Using subshell notation, give electronic configuration of K atom and K ion 3 (10)K 1s22s22p63s23p64s1 K+ 1s22s22p63s23p6 2 (11)State why 2 peaks at m/e values of 63 and 65 were obtained in a mass spectrum of an element (11)2 different isotopes 1 (12)Write equation for 5th ionisation of Na (12)Na4+(g) Na5+ (g) + e (14)The logarithm of successive IEs for Mg across the page 0 Explain what this graph tells you about the electron arrangement in the Mg atom 0 1 2 3 4 5 6 7 8 9 10 11 12 (14)Two/big jumps show 3 different shells present, shows 2.8.2 N u m b e r o f e le c tro n re m o v e d Find the empirical formula of the compound containing C 22.02% H 4.59% Br 73.39% by mass Atomic ratio Simplified atomic ratio C 22.02/12= 1.835 1.835/0.917 = 2 H 4.59/1= 4.59 1.835:4.59:0.917 4.59/0.917 = 5 Br 73.39/80= 0.917 0.917/0.917 = 1 Empirical formula is thus C2H5Br (1)Compound X contains only B and H, % by mass of B in X is 81.2% In mass spectrum of X the largest value peak of m/z is at 54 Calculate empirical and molecular formula (1)B:H = 81.2/10.8 : 18.8/1, 7.51:18.8, 1:2.5, 2:5 Empirical formula is B2H5 Mr(B2H5) = 26.6 Molecular formula = B4H10 (2)Hydrazine(empirical formula NH2)mass spectrum of this compound shows a molecular ion peak at m/e 32, show the molecular formula of hydrazine is N2H4 (2)Relative Molar Mass = 32 n(N + 2H)= 32 n(14 + 2)= 32 n= 2 Molecular formula = 2 NH2 = N2H4 Equations are: Internationally understood Quantitative Shorter than the same information given in words Equations balance for mass and total charge LHS & RHS have the same number of each type of atom, if there are 2 positives on LH there must be 2 on RHS Ionic equations: 1 Write soluble ionic compounds with the ions separated 2 Write insoluble ionic and covalent compounds as usual 3 Cross out spectator ions(ions which appear on both sides of the equation) NaCl(aq) + AgNO3(aq) NaNO3(aq) + AgCl(s) Silver nitrate silver chloride(white ppt) Ions: Na+(aq) + Cl(aq) + Ag+(aq) + NO3(aq) Na+(aq) + NO3(aq) + AgCl(s) Deleting spectator ions: Ag+(aq) + Cl(aq) AgCl(s) 2KMnO4(aq) + 8H2SO4(aq) + 10FeSO4(aq) 2MnSO4(aq) + 5Fe2(SO4)3(aq) + K2SO4(aq) + 8H2O(l) potassium manganate(VII) iron(II)sulphate Ions: 2K+(aq) + 2MnO4(aq) + 16H+(aq) + 18SO42(aq) + 10Fe2+(aq) 2Mn2+(aq) + 10Fe3+(aq) + 18SO42(aq) + 2K+(aq) + 8H2O(l) Deleting spectator ions: MnO4(aq) + 8H+(aq) + 5Fe2+(aq) Mn2+(aq) + 5Fe3+(aq) + 4H2O(l) L o g io n is a tio n e n e rg y /k J m o l 1

Avogadro constant NA is 6.02 x 1023mol1(L, Loschmidts number) - At RTP, 298K, 100kPa, 1 mol of gas occupies 24dm3 - Volumes of all gases are equal under the same conditions and contain the same number of particles - 1 mol of any substance is 6.02 x1023 particles of it is its relative molecular/atomic mass in g(molar mass, gmol1) - Fe(s) + S(s) FeS(s) Contain the same number of particles Indicator pKind pH range Half way colour Litmus 6.5 5-8 Dark purple Methyl orange 3.7 3.1-4.4 Orange Phenolphthalein 9.3 8.3-10 Pale pink