Arithmetic

Trigonometry

The BODMAS rule reminds us of the order in which operations are carried out. BODMAS stands for: Brackets () First priority

tan =

Standard triangles:

a side adjacent to = cos = a hypotenuse c adjacent side opposite to b Pythagoras theorem: = side adjacent to a a2 + b2 = c2
2 1 45 1 30 3 2 60 1

Of Division Multiplication

Second priority Second priority Second priority

opposite

When multiplying or dividing positive and negative numbers the sign of the result is given by: positive positive = positive positive negative = negative negative positive = negative negative negative = positive positive positive = positive = negative positive negative negative negative = negative = positive positive negative

Degrees and radians: 2 360 = 2 radians, 1 = = radians 360 180 180 degrees 57.3 1 radian = Trig ratios for an acute angle : e b side opposite to s u = ten po c hypotenuse c b hy sin =

1 sin 45 = , 2

3 cos 30 = , 2 cos 60 =

1 cos 45 = , 2

tan 45 = 1 1 tan 30 = 3 tan 60 = 3

1 sin 30 = , 2 3 , 2 sin 60 =

1 , 2

Braggs Law: a fundamental law of x-ray crystallography. n = 2d sin = wavelength of the x-rays incident on a crystal lattice with planes a distance d apart, n is an integer (whole number), and , the Bragg angle, is the angle between the incident beam and the reecting planes.

Matrices and Determinants

Addition + Third priority Subtraction Third priority numerator Fractions: fraction = denominator Adding and subtracting fractions: to add or subtract two fractions rst rewrite each fraction so that they have the same denominator. Then, the numerators are added or subtracted as appropriate and the result is divided by the common denomina3 16 15 31 4 + = . tor: e.g. + = 5 4 20 20 20 Multiplying fractions: to multiply two fractions, multiply their numerators and then multiply their denominators: e.g. 3 5 35 15 = = 7 11 7 11 77 Dividing fractions: to divide two fractions, invert the second 3 2 3 3 9 and then multiply: e.g. = = . 5 3 5 2 10 Proportion and Percentage: To convert a fraction to a percentage multiply by 100 and label the result as a percentage. as a percentage is 100% = 62.5%
5 8 1 3

as a percentage is

5 8 1 3

100% = 33 1 % 3

a b The 2 2 matrix A = has determinant c d a b = ad bc |A| = c d a11 a12 a13 The 3 3 matrix A = a21 a22 a23 has determinant a31 a32 a33 a23 a21 a23 + a13 a21 a22 a12 a31 a32 a33 a31 a33 a22 |A| = a11 a32

Some common conversions are: 1 1 3 1 = 10%, = 25%, = 50%, = 75% 10 4 2 4 Ratios are an alternative way of expressing fractions. Consider dividing 200 between two people in the ratio of 3:2. For every 3 the rst person gets, the second person gets 2. So the 2 rst gets 3 of the total, and the second gets 5 of the total; 5 that is 120 and 80. Generally, to split a quantity in the ratio m : n, the quantity is of the total and mn of the total. split into mm +n +n

The inverse of a 2 2 matrix: 1 a b d b If A = then A1 = c d ad bc c a provided that ad bc = 0. Matrix multiplication: for 2 2 matrices a b a + b a + b = c d c + d c + d

Remember that AB = BA except in special cases.

Graph of y = ex and y = ex Graph of y = ln x and y = log x 10 showing exponential growth/ decay

The sample unbiased estimate of standard deviation, s, is the n )2 i=1 (xi x . The standard square root of the variance: s = n1 deviation of the sample mean is called the standard error of the s mean and is equal to , and is often estimated by . n n Population values, or parameters, are denoted by Greek letters. Population mean = . Population variance = 2 . Population standard deviation = . Sample values, or estimates, are denoted by roman letters. The mean of a sample of n observations x1 , x2 , . . . xn is n x1 + x2 + + xn i=1 xi = x = n n The sample mean x is an unbiased estimate of the population mean . The unbiased estimate of the variance of these n sample n )2 i=1 (xi x which can be written as observations is s2 = n1 n 1 2 nx 2 s2 = xi n 1 i=1 n1
Removing brackets: a(b + c) = ab + ac, a(b c) = ab ac a ac (a + b)(c + d) = ac + ad + bc + bd c= b b Formula for solving a quadratic equation: b b2 4ac if ax2 + bx + c = 0 then x = 2a Laws of Indices: am = amn (am )n = amn (ab)n = an bn am an = am+n an m 1 a0 = 1 am = m a1/n = n a a n = ( n a)m a Logarithms: for any positive base b (with b = 1) logb A = c means A = bc . Logarithms to base e, denoted loge or alternatively ln are called natural logarithms. The letter e stands for the exponential constant which is approximately 2.718. loge A or ln A = c means A = ec . c, the natural logarithm of a number A, is the power to which e would have to be raised to equal A. Note: eln A = A if A > 0; ln(eA ) = A Logarithms to base 10: log10 A = c means A = 10c . pH: of a solution measures its acidity or basicity. where [H+ ] = hydrogen ion concentration in mol dm3 and c = 1 mol dm3 . Equivalently, pH = log10 aH3 O+ where aH O+ = hydronium ion activity. 3 Laws of Logarithms: for any positive base b, with b = 1, A logb A logb B = logb , logb A + logb B = logb AB, B n logb A= logb An , logb 1 = 0, b = 1. Specically, Formula for change of base: ln x log10 x = . ln 10 Inequalities: loga x = logb logb x . logb a
pH = log10 ([H+ ]/c )

a > b means a is greater than b a < b means a is less than b

a b means a is greater than or equal to b a b means a is less than or equal to b x1 ,

the sum x1 + x2 + . . . xn is written

Sigma notation: The Greek letter sigma, , is used to abbrevix , . . . xn , and add them, ate addition. If we have n values, 2 n xi .
i=1

instance

Example:

Note that i takes all whole number values from 1 to n. So, for 3 xi means x1 + x2 + x3 .
i=1

Product notation:

5 2 2 2 2 2 2 i=1 i means 1 + 2 + 3 + 4 + 5 . n xi = x1 x2 . . . xn . i=1

Produced in conjunction with the Higher Education Academy Maths, Stats & OR Network, the UK Physical Sciences Centre, sigma, and the HE STEM Programme. Thanks to the many individuals who c 2010. - version draft 1, August 2010. oered detailed advice.

Quadratic functions: y = ax2 + bx + c

Algebra

Exponential and log functions: e 2.718 is the exponential constant. y y = ex y= e-x

The straight line: y = mx + c. m=gradient (slope), c = vertical intercept.

so

[H+ ] = 10pH c

(1) (2) (3)

(x1 ,y1 )

-1

b2 4ac < 0 b2 4ac = 0 b2 4ac > 0

pos

if a is positive

gr itive

b/2a

Graphs of common functions

t dien

(x2, y2 ) y2 y1 m= x2 x1

Statistics

(1)

(2)

(3)

(1) (2) (3)

b2 4ac > 0 b2 4ac = 0 b2 4ac < 0

(x1 ,y1 )

if a is negative

neg

b/2a

ativ

e gr

adie

nt

(x2 ,y2 )

y= ln x y = log1 0 x

(1)

(2) (3)

d2 f df , means dierentiate dx 2 dx df d2 f d . with respect to x. That is, = dx 2 dx dx Partial derivatives: If f = f (x, y ) is a function of two (or more) f independent variables, x means dierentiate f with respect to means dierentiate f x treating y as if it were a constant. f y with respect to y treating x as if it were a constant.

The product and quotient rules: v du u dv dv du d u d (uv ) = u +v = dx 2 dx . dx dx dx dx v v The chain rule: dy dy u If y = y (u) where u = u(x) then d = d d . x u dx

dy Dierentiating a function, y = f (x), we obtain its derivative d . x This new function tells us the gradient (slope) of the original dy = 0 the gradient is zero. function at any point. When d x

Higher derivatives: f (x), or

The linearity rule: (af (x) + bg (x)) dx = a f (x) dx + b g (x) dx, (a, b constant) b b dv du u dx = [uv ]b Integration by parts: v dx . a d x d x a a The linearity rules: d du dv (u(x) v (x)) = dx dx dx k, constant x x2 xn , constant n sin(kx) cos(kx) ex ekx ln kx = loge kx y = f (x )

xn , (n = 1) 1 x1 = x ex ekx sin kx cos kx x2 k , constant x f (x)

1 x dy dx

0 1 2x nxn1 k cos(kx) k sin(kx) ex kekx

Dierentiation

= f (x )

Integration

c ln x + c or ln c x ex + c ekx k +c 1 k cos kx + c 1 k sin kx + c kx + c x2 2 +c

x3 3 +c xn+1 n+1 +

f (x) dx

d df (k f (x)) = k dx dx for k constant.

dy <0 dx

minimum point

dy >0 dx

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Units & Conversions

Amount of substance etc.

The partial pressure, pi , of one of the gases can be calculated by multiplying the gas mole fraction, xi , by the total pressure of all the gases, ptotal . Perfect Gas Law: pV = nRT where R = ideal gas constant. p 2 V2 p 1 V1 = . Combined Gas Laws: T1 T2 Virial equation of state: This improves the perfect gas law because it takes into account intermolecular forces. B C pVm = RT (1 + + 2 + . . .) Vm Vm Vm = V = molar volume, B, C etc are the virial coecients. n Observe that when the molar volume is very large, the terms B and VC 2 become increasingly less important, and in the limit Vm m we obtain the ideal gas law. Van der Waals equation takes into account the nite distance between molecules and interparticle attractions: an2 RT a p + 2 (V nb) = nRT p= 2 or Vm b Vm V a is a measure of attraction between particles, b is the volume excluded by a mole of particles.

Daltons Law of partial pressures: states that the pressure exerted by a mix of ideal gases is the sum of the partial pressures each would exert if they were alone in the same volume: n pi ptotal = p1 + p2 + . . . + pn or ptotal =
i=1

Scientic notation: is used to express large or small numbers concisely. Each number is written in the form a 10n where a is usually a number between 1 and 10. We make use of . . . 0.01 = 102 , 0.1 = 101 , . . . , 100 = 102 , 1000 = 103 , . . . Then, for example, 6859 = 6.859 1000 = 6.859 103 and 0.0932 = 9.32 0.01 = 9.32 102 . SI base units: for most quantities it is necessary to specify the units in which they are measured. Quantity SI unit Symbol length metre m mass kilogram kg time second s temperature kelvin K amount of substance mole mol current ampere A luminous intensity candela cd Derived units are formed from the base units. For example, the unit of force is found by combining units of mass, length and time in the combination kg m s2 . This combination is more usually known as the newton, N. Property unit name unit symbols frequency hertz Hz = s1 force newton N = kg m s2 pressure pascal Pa = N m2 energy joule J = N m = kg m2 s2 charge coulomb As potential dierence volt V = J C 1 power watt W = J s 1 Celsius temperature degree Celsius C Capacitance farad F = C V1 Resistance ohm Common prexes: a prex is a method of multiplying the SI unit by an appropriate power of 10 to make it larger or smaller.

The mole is the amount of substance that contains 6.0221415 1023 (Avogadro constant/ mol1 ) atoms or molecules of the pure substance being measured. For example 1 mole (mol) of potassium will contain NA atoms. 1 mole of water contains NA water molecules. A mole of any substance contains as many atoms or molecules (as specied) as there are atoms in 12g of 12 the carbon isotope 6 C. (To avoid confusion, always specify the type of particle.) The molar mass, M , of a substance is the mass divided by chemical amount. For pure materials, molar mass, M = molecular weight (or relative atomic or molecular mass) g mol1 . n The concentration or molarity of a solute is c = V where n = amount of solute, V = volume of solution. Molarity is usually quoted in mol dm3 . The unit 1 mol dm3 is commonly denoted 1 M and read as molar. The molality, b, of a solute is the amount of solute divided by n the mass of solvent: b = m . So, molality represents 1 mole of a solute in 1 kg of solvent. The mole fraction, x, of a solute is the amount of solute divided by the total amount in the solution: n x= . ntotal The mass density (or just density), , of a substance is its mass divided by its volume, that is = m . V The mass percentage is the mass of a substance in a mixture as a percentage of the total mass of the mixture. The mass-volume percentage is the number of grams of solute in 100 millilitres of solution. The volume-volume percentage is the number of millilitres of liquid solute in 100 millilitres of solution. Parts per million (ppm): mg/kg. Parts per billion (ppb): g/kg. Mass obtained Yield: % yield = 100 Theoretical yield

Gibbs phase rule: F = C P + 2, where F is the number of degrees of freedom, C = number of independent components, P = the number of phases in equilibrium with each other. This is a relationship used to determine the number of state variables, F , chosen from amongst temperature, pressure and species compositions in each phase, which must be specied to x the thermodynamic state of a system in equilibrium. Clapeyron equation relates change in pressure to change in temperature at a phase boundary. The slope of the phase dp boundary is d . dp H T = dT T V Here H = molar enthalpy of transition, V = change in molar volume during transition.

Gases

The general form of an equation of state is p = f (T, V, n) where p = pressure, T is temperature, V = volume, n = amount of substance. Boyles Law relates the pressure and volume of a gas when the temperature is xed: p1 V1 = p2 V2 . 1 An equivalent form is: pV = nM c2 , where n = number of 3 molecules, m = mass of a molecule, M (= mNA ) is the molar mass of the molecules, c2 = mean square speed. Charless Law relates the volume and temperature of a gas at V1 T1 = . V2 T2 constant pressure:

Multiple Prex Symbol Multiple Prex Symbol 1012 tera T 101 deci d 109 giga G 102 centi c 106 mega M 103 milli m 103 kilo k 106 micro 102 hecto h 109 nano n 101 deca da 1012 pico p Interconversion of units: Sometimes alternative sets of units are used and conversion between these is needed. Pressure is often quoted in units corresponding to the Standard atmosphere (atm). Then 1 atm = 1.01325 105 Pa = 1.01325 bar = 760mm Hg = 760 Torr. (1 bar = 1 105 Pa). ngstr where Length (of bonds) is sometimes quoted in A oms, A 1 A = 1010 m. 1 nm = 109 m. 0.1nm=100pm. Energy is often measured in calories (cal): 1 cal = 4.184 J.

Here H = molar enthalpy of vaporisation. This equation relates the natural logarithm of the vapour pressure to the temperature at a phase boundary.

Clausius-Clapeyron equation is an approximation of the Clapeyron equation for a liquid-vapour phase boundary. Plotting vapour pressure for various temperatures produces a curve. For 1 pure liquids, plotting ln pp against T produces a straight line H with gradient . (Here, p = any standard pressure). R p1 H 1 1 = p2 R T1 T2 ln

Vm,i is the partial molar volume of the ith substance. Total Gibbs energy for the mixture is G = nA GA + nB GB where GA and GB are the partial molar Gibbs energies of substances A and B respectively. The partial molar Gibbs energies are also denoted A and B so that G = nA A + nB B . More n i i . generally, with mixtures of several substances G =

where Vm,A = partial molar volume of A and Vm,B = partial ni Vm,i , where molar volume of B . More generally, V =

Standard state: The standard state of a substance is the pure substance at a pressure of 1 bar. The standard state value is denoted by the superscript symbol , as in G . G Reaction Gibbs energy: r G = is the slope of the graph of Gibbs energy against the progress of the reaction. Here, = nJ /J for all species J in the reaction. Reaction Gibbs energy at any composition of the reaction mixture can be written v r G = r G + RT ln Q where Q = aJ J

where A = chemical potential of pure A and xA is the mole fraction. Properties of mixtures: suppose an amount nA of substance A is mixed with nB of substance B . The total volume of the mixture is V = nA Vm,A + nB Vm,B

Raoults law: states that the partial vapour pressure, pA , in a liquid mixture, A, is proportional to its mole fraction, xA , and its vapour pressure when pure, p p A = xA p A: A. Henrys law: states that the vapour pressure, pB , of a volatile solute, B , is proportional to its mole fraction, xB , in a solution: pB = xB KB . Here KB is Henrys law constant. Chemical potential of a solvent: A = A + RT ln xA

Phases

vant Ho equation:

where aJ is the activity of species J and J is its stoichiometric number.

= RT ln K At equilibrium Q = K , r G = 0 and r G where v K= (aJJ )equilibrium

Reaction Thermodynamics

d r H . ln K = dT RT 2 K2 1 r H 1 ln = K1 R T2 T1

Mixtures

Order

Rate Laws In the table, [A] = molar concentration of reactant A at time t. [A]0 = concentration of reactant A at time t = 0.

where k = rate constant, Ea = the activation energy for the reaction, R = ideal gas constant, T = absolute temperature, and A is a constant. By taking logarithms this can be expressed as A Ea k = ln ln k k RT where k is a chosen standard rate constant. Together, A and Ea are called the Arrhenius parameters.

(* A + B P reaction.)

If a = a1 i + a2 j + a3 k and b = b1 i + b2 j + b3 k then

If r = xi + y j + z k then |r| =

Arrhenius equation: The rate at which most chemical reactions proceed depends upon the temperature. The amount of energy necessary for the reaction to take place at all is called the activation energy. These quantities are related by the Arrhenius equation: k = AeEa /(RT )

a b = |a| |b| sin e

Vector product:

a b = |a| |b| cos

Scalar product:

is a unit vector perpendicular to the plane containing a and e b in a sense dened by the right hand screw rule. If a = a1 i + a2 j + a3 k and b = b1 i + b2 j + b3 k then

ab

Rate Law Dierential form

d[A] dt

d[A] dt

d[A] dt

d[A] dt

= k[A][B ] = = = k[A]2 = k[A] = k

(a 2 b3 a 3 b2 ) i + ( a 3 b1 a 1 b3 ) j + ( a 1 b2 a 2 b1 ) k i j k a1 a2 a3 b1 b2 b3

a b = a 1 b1 + a 2 b2 + a 3 b3

1 [B ]0 [A]0 1 [A]

Rate Law Integrated form

[A]0 [A] = kt

[A] = [A]0 ekt

Kinetics

Vectors

1 [A]0

= kt ln x2
e
[B ][A]0 [A][B ]0

= kt + y2

z2 .

Half-life

1 k[A]0

[A]0 2k

ln 2 k

b a

mol1 dm3 s1 mol1 dm3 s1 mol dm3 s1 Common unit of k s 1

First Law: For a closed system, U = q + w. Here U is the change in internal energy of a system, w is the work done on the system, and q is the heat energy transferred to the system. Enthalpy: H = U +pV where U = internal energy, p=pressure and V = volume. Heat capacity at constant volume: CV = U V T Heat capacity at constant pressure: Cp = H T p In general Cp depends upon T . Values of Cp at temperatures not much dierent from room temperature can be estimated c from Cp = a + bT + 2 T where a, b and c are experimentally determined constants. Second Law of thermodynamics: During a spontaneous change, the total entropy of an isolated system and its surroundings increases: S > 0. For a reversible process, at constant temperature, T , change in entropy qrev S = T where qrev = energy reversibly transferred as heat. Boltzmann formula: S = kB ln W where W = weight of the most probable conguration of the system and kB is the Boltzmann constant. Helmholtz energy: A = U T S . Gibbs energy: G = H T S . Change in Gibbs energy: G = H T S (at constant temperature). Entropy change for isothermal expansion of an ideal gas: Vnal S = nR ln Vinitial A B E Z H Avogadro constant Boltzmann constant Planck constant Elementary charge Ideal gas constant Vacuum permittivity Speed of light (vacuum) Faraday constant alpha beta gamma delta epsilon zeta eta theta

initial volumes. where Vnal and Vinitial are the and nal H G = 2 . Gibbs-Helmholtz equation: T T T p

General Thermodynamics The Greek alphabet Physical constants

I K M N O o iota kappa lambda mu nu xi omicron pi NA = 6.022 1023 mol1 kB = 1.381 1023 J K1 h = 6.626 1034 J s e = 1.602 1019 C R = 8.314 J K1 mol1 0 = 8.854 1012 J1 C2 m1 c = 2.998 108 m s1 F = e NA = 96.485 kC mol1 P T X rho sigma tau upsilon phi chi psi omega