Basic Physical Chemistry. Prof. Paul D.I.

Fletcher 7 lectures and 1 additional slot in semester 2 of year 1 as part of module 06512 Foundations of Chemistry 2) The aims of this segment of the module are to introduce the key concepts of: states of matter, intermolecular forces, ideal gas behaviour, equilibrium constants, enthalpy, entropy and free energy, reaction rates. rate constants and activation energy electromagnetic spectrum and spectroscopy. This module segment will also emphasise key skills in physical chemistry such as units, powers of 10 and quantitative problem solving. Synopsis (approximately by lecture) Lectures 1 & 2. States of matter and intermolecular forces. Ideal gas behaviour Lectures 3 & 4. Equilibrium constant and its relation to enthalpy, entropy and free energy. Lectures 5 & 6. Reaction rates, rate constants and rate laws. First and second order reactions and their integrated rate equations, activation energy and variation of rate with temperature. Lecture 7. The electromagnetic spectrum and spectroscopy. Energies and molecular processes occurring with microwaves, infrared, visible, UV and X ray photons. Lect/Sem 8. Completion of lectures and revision of key points Support and Assessment This module segment will include several short tests to help you check whether you have grasped the main concepts. Module 06512 will be assessed in a 2 hour exam with 4 questions, one each on the organic, inorganic, analytical and physical sections of the module. You will answer all 4 questions, each of which will have some choice in its parts. Seminars and tutorials forming part of module 06514 (Chemical & Professional Skills A) will include problem solving exercises related to this course. You will also do one session per week of physical chemistry practical in weeks 3-6. Texts P.W. Atkins and J. de Paula, Atkins Physical Chemistry OUP, 7th Edition, Oxford Good choice for your main physical chemistry text if you are OK at maths. P.W. Atkins, The Elements of Physical Chemistry, OUP Simplified version of the main Atkins text for those who struggle with the maths. K.J. Laidler and J.H. Meiser, Physical Chemistry, Houghton Mifflin Co., 3rd Edition, Boston. Good alternative to Atkinss main text. Page 1 of 1
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

States of Matter Property Size and shape Order Solid Fixed size and shape Long-range order over 100s of atoms or molecules high densities, typically 1-10 g cm-3. incompressible (almost) atoms or molecules are touching, i.e. separation = size. Liquid Fixed size but takes shape of container Only short range order over 1 2 neighbour atoms or molecules high densities, typically 1-10 g cm-3. incompressible (almost) atoms or molecules are touching, i.e. separation = size. Gas Takes the size and shape of the container No order at all

Density Compressibility Atom or molecular separation

low densities, typically 0.1 to 0.001 g cm-3 very compressible atoms or molecules are separated by many atom or molecular diameters

Pictorially (in 2 D):

Solid Rigid lattice Long range order Atoms/molecules touching

Liquid No rigid lattice Short range order Atoms/molecules touching

Gas No rigid lattice No order Atoms/molecules very widely separated

Phase transitions between different states of matter occur at sharply defined temperatures and pressures with taking in or giving out of heat (at constant pressure this heat change is the enthalpy change). For example, for pure water at 1 atm pressure: 0oC, 60.2 kJ mol-1 ice 20 cm3 water 18 cm3 Page 2 of 2
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

100oC, 40.7 kJ mol-1 steam at 1 atm 30618 cm3

NB. Water is very unusual in that the solid form (ice) is less dense than the liquid form (water). This behaviour is due the structuring of liquid water caused by hydrogen bonding. Phase transition temperatures depend on pressure. Increasing the pressure causes the lowest volume form (i.e. the highest density)of the material to be formed formed more easily. For example, increasing the pressure to more than 1 atm will cause water to boil at a temperature higher than 100oC. High pressures will make ice melt to water at temperatures lower than 0oC. This last effect is why ice skating works. The high pressure of an ice skate blade on the ice causes the ice to melt enabling the blade to slip over a thin film of liquid water. The thin film of liquid water re-freezes when the ice skate blade is removed. Note that skating would not work on the frozen forms of materials other than water. Because these solids are more dense than the corresponding liquid forms, high pressure has the opposite effect on the melting points of such solids i.e. it causes increased freezing rather than melting. The graph below shows how the temperature varies as heat is supplied at a constant rate into a fixed mass of H2O at a pressure of 1 atm which is initially frozen ice at -50oC. The heat supplied raises the temperature of the water.
200 150 temperature/oC 100 50 0 -50 0 2 4 time/arbitrary units 6

The heat supplied coverts the ice to water at 0oC.

The heat supplied converts the water into steam at 100oC

The heat supplied raises the temperature of the ice.

The heat supplied raises the temperature of the steam.

For a particular substance, the state of matter is determined by the balance between inter-molecular force energy (a potential energy which depends on the atomic/molecular positions and can be changed by pressure) and the kinetic energy of Page 3 of 3
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

the atoms/molecules (kinetic energy is determined by atom/molecule velocities) and is controlled by temperature. Gases favoured by high temperatures, low pressures (corresponds to large atom or molecule separations) and intermolecular forces in which repulsion is stronger than attraction. Solids favoured by low temperatures, high pressures (corresponds to small atom or molecule separations) and intermolecular forces in which attraction is stronger than repulsion. Inter-molecular Forces & Energies Some key points to understand first. Energy = force x distance moved (when the force is constant). In terms of units, 1J = 1Nm Inter-molecular forces are weaker than intra-molecular forces (covalent, ionic or metallic bonds. In terms of energies, this means that the energy needed to break one mole of inter-molecular bonds is much less than the energy needed to break one mole of intra-molecular bonds, e.g. C-C bond energy is approximately 440 kJ mol-1. Inter-molecular forces become weaker when the separation between atoms or molecules is increased. They are zero when the separation is infinite (approximately true for a gas at low concentration). Because the energy associated with inter-molecular forces depends on the atom/molecule positions, the energy is a potential energy. The energy required to pull atoms or molecules apart from a certain separation to infinite separation is positive (requires energy input) when the net force is attractive and negative (gives energy out) when the net force is repulsive. The energy needed to break all the inter-molecular forces in a material is the energy required to turn it into a gas where all the molecules are widely separated and inter-molecular forces are negligibly small.

The basis for all intermolecular forces can be understood in terms of the rules of electrostatics Like charges repel Unlike charges attract Inter-molecular forces depend on the net charge and charge distribution of the interacting atoms or molecules and can be summarised under the following headings. Ion-Ion Example: Na+ with ClEnergy of interaction = +40-400 kJ mol-1 (depends on solvent) The + sign indicates that can be attractive or repulsive.

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

Digression about permanent dipole moments (dipoles). Uncharged molecules can be polar or apolar. In a molecule such as ethane where all the atoms have similar electronegativities, then the charge distribution is even over the whole molecule which is then described as apolar. In a molecule such as chloroethane, the chlorine atom is more electronegative than the other atoms and tends to attract more than its fair share of electrons to itself. This uneven electron distribution causes the chlorine end of the molecule to be slightly negative and the other end to therefore be slightly positive. This type of molecule is polar and has a permanent dipole moment. The word permanent here means that the dipole moment remains in the absence of an applied electric field. The chlorine end of the chloroethane molecule has a small negative charge (units = Coulomb C) and the other end has a slight positive charge. CH3 CH3 Apolar CH3 CH2Cl Polar

The dipole moment has the following definition. For a particle which has one end with a charge of +q and the other end with a chage of q with a separation of x between them, then the dipole moment is qx and has units of Cm. How big is a dipole moment? We can estimate the order of magnitude very roughly as follows. Intuitively we might expect that the charge on one end of a polar molecule might be (say) 10% of one electron (electronic charge = -1.602 x 10-19 C). The separation will be roughly one bond length which is about 0.1 nm. Assuming these values, we get that a typical dipole moment will be about 1.6 x 10-30 Cm. It can be more convenient to use Debye units for dipole moments where 1 D is equal to 3.336 x 10-30 Cm. Our estimated dipole moment is therefore of the order of 0.5 D. Compare this order-of-magnitude estimate with actual values for molecules in the gas phase as shown in the table below. As you can see, the order of magnitude of the actual dipole moment values observed do indeed correspond to charges equal to a fraction of an electron separated over a distance comparable to a typical bond length. molecule Dipole moment/D water 1.85 chloroethane 2.05 Carbon dioxide 0 Cyanoethane (= propionitrile) 4.02 Question: Can you work out why water has a non-zero dipole moment whereas carbon dioxide does not? Ion-Dipole Example: Na+ with H2O Energy of interaction = 4-40 kJ mol-1 (always attractive) In this example, the positive sodium ion is attracted to the negative end of the water molecule (i.e. the oxygen atom). A negative ion is attracted to the positive end of a dipole. Attractive ion-dipole forces between ions and polar solvents such as water are the reason why salts are soluble only in polar solvents. Page 5 of 5
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

Dipole-Dipole Example: Chlorobenzene with Chlorobenzene Energy of interaction = 0.4-4 kJ mol-1 (always attractive) The molecules rotate until the negative end of one (the Cl atom in this example) is aligned with the positive end of another which has the result that the force is always attractive. Hydrogen bond The hydrogen bonds is an especially strong case of a dipole-dipole interaction which occurs between H and electronegative atoms such as O, N, F, Cl, etc. We can represent it as follows. R-E-H..E-R where E and E are electronegative atoms and R and R represent the rest of each of the molecules. The H bond is represented as the dotted line. Example: water with water Energy of interaction = 10-40 kJ mol-1 (always attractive) The H bond is particularly strong because the H atom has only one electron surrounding its nucleus consisting of a single proton. When the single electron gets pulled towards the electronegative atom, it leaves the proton of the H atom unshielded where its positive charge can interact strongly with the negative charged end of the second molecule. When outer-shell electrons are pulled away from atoms other than hydrogen, there are always inner-shell electrons shielding the nucleus. Dipole-Induced dipole When a molecule which is uncharged and has no permanent dipole moment is placed in an electric field, the electron distribution is distorted by the electric field to give an induced dipole which goes to zero when the electric field is removed. The electric field can be applied by electrodes (electric field = voltage difference divided by electrode separation, units V m-1), by being close to a charge or another dipole or by electromagnetic radiation (= an oscillating electric and magnetic field). The size of an induced dipole depends on the magnitude of the applied electric field and the polarisability of the molecule. Molecules such as benzene which contain their outermost electrons in big, delocalised orbitals (i.e. electrons are far from the positive nuclei and therefore weakly held) are relatively highly polarisable. Example: Chlorobenzene (permanent dipole) with benzene (no perm. dipole) Energy of interaction = 0.4-4 kJ mol-1 (always attractive) When close together the permanent dipole induces the opposite sign dipole in the other molecule. Hence the force is always attractive. Dispersion forces (also called London forces after their discoverer). Even molecules with no permanent charges or dipoles attract each other. For example, we know that He attracts He because it is possible to liquefy the gas at low enough temperatures. How does this attraction work when we know that the average electron distribution in the 1s orbitals is spherically symmetrical? The answer is that Page 6 of 6
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

the electrons are moving from one end of the atoms the other on a timescale of approximately 10-15 seconds. On this very fast timescale the atoms will have instantaneous transient dipoles which are continuously changing direction. When two He atoms are close you might think that their transient dipoles will spend as much time repelling (when dipoles are aligned) as attracting (when dipoles are opposite) so that the time-average net force is zero. However, when they are close the transient dipoles interact and tend to change direction synchronously such that there is a net time-average attraction. This should not be too surprising as you would expect the system to do whatever gives the lowest energy. The net result is that there is always an attractive force. Because all molecules have electrons which are moving, all molecules have attractive dispersion forces. Example: Helium with Helium Energy of interaction = 0.4-40 kJ mol-1 (always attractive, bigger for bigger molecules) Short-range repulsion When molecules or atoms are very close together (i.e. the separation is approximately equal to the size of the outermost electron orbitals, typically less than 0.15 nm) then the electron clouds repel each other very strongly. This short range repulsion increases very strongly if you try to push the atoms closer. This short range repulsion is why things feel solid. When you look at atomic diagrams it is obvious that the actual nuclei and electrons occupy only a small fraction of the actual space taken up by atoms and molecules. Most of this space occupied by molecules is empty! The reason you cannot push your hand through a wall is that the electron clouds of the atoms of your hand feel a strong short range repulsion with the electron clouds of the atoms of the wall. Inter-molecular interaction energy diagram As we have seen, all molecules interact with a mixture of attractive and repulsive forces. We can represent this as a plot of the energy required to bring the molecules to a certain separation from infinite separation where the interactions are zero. In such a plot (shown below), negative energies correspond to attractive forces and positive energies correspond to repulsive forces. The force between the molecules at a particular separation is given by the slope of the plot, i.e. it is equal to the differential d(energy)/d(separation). The negative slope region corresponds to a repulsive force and the positive slope region to an attractive force. At the separation corresponding to minimum energy, the force (= slope) is zero and hence this is the equilibrium separation of the two atoms or molecules. At an absolute temperature T, the thermal or kinetic energy of a molecule is kT where k is Boltzmanns constant. For a mole of molecules, the thermal energy is NkT where N is Avogadros number. The product Nk is equal to the gas constant R (equal to 8.314 J mol-1 K-1) and hence the thermal energy of one mole of molecules is RT. At room temperature, this thermal energy of a mole of molecules is roughly 2.5 kJ mol-1. Page 7 of 7
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

How does the inter-molecular interaction energy diagram determine whether a particular material is a solid, liquid or gas at some particular absolute temperature? It depends how deep the interaction energy minimum is relative to the thermal energy. If the interaction energy minimum is large compared with thermal energy then no molecules have enough thermal energy to escape from the energy minimum. Hence, all molecules will have a separation corresponding to the equilibrium separation and the material will be a liquid or solid. If the minimum is small compared with the thermal energy, then the thermal energy is enough to enable the molecules to escape from the minimum to infinite separations, i.e. to form a gas. Gases will be formed when either (a) the attractive interaction energy is weak or (b) when the thermal energy is high by increasing the temperature. Obviously all molecules fall to the bottom of the energy minimum when the absolute temperature is zero.
0.2

energy required to bring the molecules fro infinite separation/arbitrary units

0 0 -0.2 0.5 1 1.5 2 2.5

-0.4

-0.6 typical separation/nm

Ideal gas behaviour All gases behave ideally under conditions when all inter-molecular forces are negligible. These forces include long-range attraction and short-range repulsion. All inter-molecular forces become negligibly small when all the atoms or molecules are a long way apart and the actual space occupied by the gas molecules is negligible compared with the overall volume of the gas. This happens when the concentration (=n/V) of the gas is low which, at fixed moles, temperature and volume, can be achieved by decreasing the pressure. How weak do inter-molecular forces have to be to be negligible? Intermolecular forces are insignificant if they are not strong enough to attract or repel the gas molecules away from completely random flight paths. This is true when the potential energy of the inter-molecular forces (i.e. the energy needed to pull the molecules against their inter-molecular forces to infinite separation) is small relative to the Page 8 of 8
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

thermal or kinetic energy (= RT for one mole) making the gas molecules fly about. Hence, the inter-molecular forces can be made negligibly small in tow ways. Firstly, you can weaken the forces by separating the gas molecules by lowering the concentration as described above. Secondly, you can raise the thermal energy by increasing the temperature. In summary, gases behave ideally in the limits of low pressure and high temperature. They deviate from ideal behaviour more and more as you increase the pressure and/or lower the temperature, i.e. as you move towards condensing the gas into a liquid. Whether or not the assumption of ideal gas behaviour is OK for a particular calculation depends on how accurately you need the answer. Gases are likely to behave reasonably ideally when the pressure is lower than one atmosphere and the temperature is more than 100oC above the normal boiling point of the liquid. When gases are ideal, they obey the following equation PV = nRT where P is pressure, unit Pa (1 Pa = 1 N m-2) V is the total volume of the gas, unit m3 n is the number of moles of the gas, unit mol R is the Gas constant, equal to 8.314 J mol-1K-1 T is the absolute temperature, unit K (equal to oC + 273.15) Hint. As for all equations, you can check this equation is correct by testing that the units of the LHS and RHS are equal. LHS of equation PV units are N m-2 m3 = N m = J RHS of equation nRT units are mol J mol-1 K-1 K = J Units match and so the equation is OK. Sample calculation An ideal gas has a pressure of 400 mm Hg in a container of volume 300 cm3 at a temperature of 25oC. What will the pressure be if the temperature is raised to 100oC? [The gas constant R = 8.314 J mol-1 K-1] Long method answer Since PV = nRT, we can re-arrange to get P = nRT/V. In order to calculate the new pressure P at 100oC, we have to first calculate the number of moles n using the known pressure at 25oC. By re-arranging the equation we get n = PV/RT. Converting all units to SI units will give n in units of mol. P = 400 mm Hg = 400/760 atmosphere = (400/760) x 101325 Pa = 53329 Pa T = 25oC = 298.15 K V = 300 cm3 = 300 x 10-6 m3 Hence, n = (53329 x 300 x 10-6)/(8.314 x 298.15) = 6.454 x 10-3 mol We now use this value of n to calculate P at 100oC (= 373.15 K) P = nRT/V = (6.454 x 10-3 x 8.314 x 373.15)/(300 x 10-6) = 66742 Pa We can convert this pressure back into units of mm Hg. P = 66742 Pa = (66742/101325) atmosphere = (66742/101325) x 760 mm Hg P = 500.6 mm Hg

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

Short method answer Re-arranging PV = nRT gives P/T = nR/V which is a constant if the number of moles and volume is kept constant as they are in this problem. If we have two values (P1 at T1 and P2 at T2), then P1/T1 = constant = P2/T2. Putting in numbers gives: 400/298.15 = P2/373.15 Re-arranging gives P2 = (400/298.15) x 373.15 = 500.6 mm Hg. Note here that P2 comes out in the same units as those used for P1 (i.e. mm Hg used here). The final answer by this much quicker method is, of course, the same as above. P = 500.6 mm Hg Equilibrium constants For any chemical reaction when equilibrium is reached and the concentrations stop changing, the ratio of the equilibrium activities or concentrations of the products divided by the equilibrium activities or concentrations of the reactants is equal to a constant called the equilibrium constant K. For any reaction, the true, thermodynamic equilibrium constant K is equal to the equilibrium activities of all the product species divided by the equilibrium activities of all the reactant species. For the particular example reaction below: A+B+C+D X+Y+Z K is equal to

K=

a X aY a Z a A a B aC a D

where aX is the activity of the species X. The activity of a species is its actual activity divided by its activity at a standard concentration which we choose. The standard concentration is called the standard state and is usually chosen to be 1 M for solutes in solution. Note that activity defined in this way is actually dimensionless but requires that the standard state should be specified. However, you are likely to see statements like activity = 0.1 M. This is a shorthand way of saying that the activity is 0.1 of the activity of the same species when in its standard state of 1 M. Because activity is unitless, all true thermodynamic equilibrium constants are also unitless. When apparent units are shown, they actually indicate the standard state which has been assumed. When we choose 1 M as the standard state and the solute behaves ideally, then the activity is numerically equal to the concentration in M units. For real solutions which do not behave completely ideally, then concentration is only approximately numerically equal to activity. For normal approximate work, we can ignore nonideality effects and equate activity and concentration. With this approximation, the equilibrium constant for the reaction above is

K=

[X ][Y ][Z ] [A][B][C ][D ]

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

As written in terms of concentrations, K for this reaction formally has units of M-1. However, these units are better regarded as a label telling you that the standard states which have been chosen for the solutes A, B, C, D, X, Y and Z are all 1 M. Equilibrium constants tell you about the extent to which a reaction will proceed if given enough time to reach equilibrium. How far a reaction will go can also be expressed in terms of the reaction yield. Hence, it should be clear that K and yield are related as illustrated below. Let us consider the simple reaction A B for which K =

[B] . [A]

We can then calculate

the yields we would get for different values of K assuming that we start the reaction with an initial concentration of A equal to [A]0. The equations we use are shown below. Initial concentration of A is [A]0 and the initial concentration of B is zero Therefore, [A] = [A]0 [B] and hence

K=

[B] = [B] and re-arranging gives [B ] = K [A]0 {1 + K } [A] {[A]0 [B ]}

The equilibrium yield is equal to [B]/[A]0 The table below shows a set of values calculated for [A]0 = 1 M. It can be seen that a [B] corresponds to a high reaction yield at equilibrium. high value of K = [A] K 0.01 0.1 1 10 100 1000 Equilibrium [A] 0.9901 0.909 0.5 0.091 0.0099 0.000999 Equilibrium [B] 0.0099 0.091 0.5 0.909 0.9901 0.9990 Equilibrium yield/% 0.99 9.1 50.0 90.9 99.0 99.9

Equilibrium constants provide a measure of the extent to which a reaction will go forward if left long enough to reach equilibrium. Whether or not a reaction will go forward depends on the difference in energies between the reactants and products and so equilibrium constant must be related to these energy differences. Consideration of these energies is the realm of thermodynamics.
Enthalpy H

Enthalpy change H (delta H) is the heat change of a process or reaction measured at constant pressure. Heat given out (the beaker gets hot) means the reaction is
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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

exothermic and, by convention, H is negative. Heat taken in (the beaker gets cold) means the reaction is endothermic and H is positive.
For reactions H is normally quoted per mole of reaction as written proceeding left to right. The units of H are J mol-1 or kJ mol-1. Consider a reaction: A B for which H = -100 kJ mol-1

If you allow 0.1 mol of A to react to give 0.1 mol of B, then the actual measured enthalpy change will 0.1 x (-100) = -10 kJ (not kJ mol-1). This is negative and so corresponds to heat given out. The enthalpy change H is simply (Hproducts Hreactants) and equals (HB HA) for the reaction shown above. The H value refers to the chemical reaction as written and hence, the H for the reverse reaction B A must be +100 kJ mol-1. Enthalpy change in a chemical reaction comes from bond making and bond breaking and so is related to the relative strengths of the chemical bonds in the products and reactants of the reaction. Making bonds releases heat and gives an exothermic reaction whereas breaking bonds requires heat input (endothermic). Note that only enthalpy changes H can be measured directly. Individual H values for separate chemicals cannot be measured directly. However, we can define a zero point that the enthalpy of a pure element in its most stable form at 298.15 K and 1 atm = 0. Relative to this zero point that we have defined, we can then measure the enthalpy of a compound. For example, the enthalpy of CO2 at 298.15 K and 1 atm will be equal to the measured H for the reaction C(diamond) + O2 (gas) CO2(gas) since the measured H = (Hproducts Hreactants) = (HCO2 - (Hdiamond + Hoxygen)) = HCO2 since both Hdiamond are Hoxygen are zero by definition. Although this can seem subtle and hard to understand, in fact it is the same process that we use to define altitude. We can only directly measure altitude differences and so we define the altitude of sea level as being zero. The altitudes that are listed on maps are equal to the altitude differences between the relevant point on the map and sea level. Similarly, individual enthalpies of chemical compounds correspond to the enthalpy differences for the reactions in which the compounds are formed from the most stable forms of their elements.
Hesss Law

This can be expressed in several different ways. The overall enthalpy (or heat) change for a process or reaction is equal to the sum of the enthalpy (or heat) changes for all the individual steps. Enthalpy is a state function, i.e. the enthalpy change depends only on the initial and final states and not on the path taken. Hesss Law can be used to calculate enthalpy changes for reactions from the enthalpy changes of the individual steps. Page 12 of 12
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

Example. The heats of combustion of ethane(g), carbon(s) and hydrogen(g) are -1558, -393 and -285 KJ mol-1 respectively. Calculate the enthalpy of formation of ethane from its elements. Answer. From the question, we know:
1. 2. 3. C2H6 + 3.5O2 2CO2 + 3H2O C + O2 CO2 + H2 + 0.5O2 H2O

H = -1558 kJ mol-1 H = -393 kJ mol-1 H = -285 kJ mol-1

We wish to know the enthalpy change for the formation reaction: 2C + 3H2 C2 H6

H = ? kJ mol-1

We can obtain the target formation reaction by taking the following combination of reactions 1 3. (2 x reaction 2) + (3 x reaction 3) (1 x reaction 1) which gives: 2C + 2O2 + 3H2 + 1.5O2 + 2CO2 + 3H2O 2CO2 + 3H2O + C2H6 + 3.5O2 We then cancel all species which appear on both the LHS and RHS to give the final reaction which we can see agrees with the target reaction. 2C + 3H2 C2H6 We then combine the H values for the individual reactions in precisely the same way as we did for the reactions, i.e.

H = (2 x -393) + (3 x -285) (1 x -1558) H = -83 kJ mol-1

Does enthalpy change alone decide whether or not a reaction will proceed forwards?

This is the same as asking whether reactions or processes will only proceed if they are exothermic more or stronger bonds are formed relative to the ones that are broken The answer is NO. Enthalpy change alone does not predict whether a reaction will proceed. The following are all examples of reactions or processes which proceed in spite of being enthalpically unfavourable (i.e. endothermic with H positive). 1. 2. 3. 4. Hg2Cl2(s) + H2(g) 2Hg(l) + 2HCl(g) SOCl2(l) + H2O(l) SO2(g) + 2HCl(g) Liquid gas some salts + water aqueous solution

Why do these reactions or processes all proceed even though they cost enthalpy? We can see a clue by looking at the states of matter in all the examples. Page 13 of 13
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

1. 2. 3. 4.

(s) + (g) (l) + (g) (l) + (l) (g) + (g) (l) (g) (s) + (l) (l)

In each of these examples there is a net change from (s) (l) or(l) (g). In all cases there is a loss of order which corresponds to an increase in randomness. Clearly, in addition to H, there must be a function related to this randomness or disorder which acts to determine whether reactions proceed. This function is called entropy S and

S = Sproducts Sreactants
When S is positive, it means the products are more disordered than the reactants and this favours the reaction proceeding forward. When S is negative, it means the products are less disordered than the reactants and this disfavours the reaction proceeding forward. (N.B. This is the opposite way round to H for which a negative value favours reaction.) As we shall see, the equilibrium position of reactions is determined by a combination of H and S which is called Gibbs Free Energy G G = H TS (where T is the absolute temperature) G = (Gproducts Greactants) = H - TS The product TS has units of energy per mol (like H since quantities can only be added together if they have the same units). Hence, S and S have units of J mol-1K-1. G is the Gibbs free energy change for one mole of reaction proceeding in the forward direction as written.
Gibbs free energy and equilibrium constant

All reactions are reversible, albeit to an infinitesimally small extent for some examples. In principle, every reaction can be made to go either forwards or backwards to reach its equilibrium ratio of concentrations by starting at different concentrations of reactants or products. For example, consider the reaction A B with equilibrium constant K = 1 If we start the reaction by taking a solution initially containing 1 M of A with zero B. The reaction will then proceed forward (i.e. A will form B) with the concentration of A dropping and the concentration of B increasing. The reaction will stop when both concentrations are equal to 0.5 M and the ratio [B]/[A] = 1 = K. Alternatively, we can start the same reaction by taking a solution initially containing 1 M of B with zero A. In this case, the reaction will proceed backwards until the same equilibrium concentrations are reached. It is important to understand that reactions can be driven to go either forwards or backwards by changing concentrations.

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

G determines whether a reaction will proceed forwards or backwards. It can be shown (see Dr. Paunovs course on thermodynamics) that:
If G = +ve, the reaction will proceed right to left (i.e. backwards) If G = 0, the reaction will be at equilibrium If G = -ve, the reaction will proceed left to right (i.e. forwards)

Accepting this, then it is clear from our previous discussion that G must depend on the concentration of a species. If changing concentrations can drive reactions either forwards or backwards, then it must also change the sign of G. G is a measure of the free energy per mol of a species which it has available to push chemical reactions. Because G is expressed per mole, its value does not depend on how much solution you have. For example, the G of a species A in 1 ml of a 1 M solution of A is identical to its G value in 100 litres of 1 M solution. However, G does depend on the concentration of A. We know that high concentrations are better at making reactions proceed and hence we expect G to be higher for higher concentrations. The relationship is as follows. G = Go + RTln(C/Cstandard state) where G is the Gibbs free energy of one mole of a species at concentration C R is the gas constant (= 8.314 J mol-1 K-1) T is the absolute temperature Cstandard state is the standard state concentration (which we can choose and which we normally take to be 1 M for species in solution). Go is the standard Gibbs free energy and is equal to the Gibbs free energy of one mole of a species at concentration equal to Cstandard state.

We can now work out the relationship between G and equilibrium constant K. Consider the reaction A + B C with equilibrium constant K Let GA, GB and GC be the Gibbs free energies per mole for species A, B and C. The G for 1 mole of the reaction in the forward direction as written is

G = GC (GA + GB)
We can write equations for each of the G values in terms of the concentrations of each. Note that we have not included Cstandard state in these equations because we are taking it to be 1 M. These equations are then substituted into the equation for G.
o GA = GA + RT ln C A
o GB = GB + RT ln C B o GC = GC + RT ln CC

o o o G = GC GA + GB + {RT ln CC (RT ln C A + RT ln C B )}

)}

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

G = G o + RT {ln CC (ln C A + ln C B )} C G = G o + RT ln C C AC B G = G o + RT ln Q This last equation tells you what G would be for any ratio of product and reactant concentrations (equal to Q). Inspection of this equation shows that if we make the product concentrations high and reactant concentrations low, then Q is large, ln Q is large and positive and so G will be positive. In this situation, the reaction will go backwards. If we make the product concentrations low and the reactant concentrations high, then Q will be less than 1 and lnQ will be large and negative. This will make G negative and hence the reaction will go forward. We can see that the equation correctly predicts what we already know. We have a special situation when the reaction reaches equilibrium. At equilibrium, we know the following: G = 0 The general concentration ratio Q = the equilibrium constant K 0 = G o + RT ln K and hence vant Hoff equation G o = RT ln K

This important equation tells us that we can relate K to Go. Go is what G would be if all reactant and product concentrations were all equal to the standard state concentration. The sign of Go tells whether the reaction will go forwards or backwards if all reactant and product concentrations were all equal to the standard state concentration. When the concentrations are equal to the equilibrium concentrations G is always zero. Obviously, you need to take care not to write G when you mean Go and vice versa. Why do we bother to compile tables of Go values for different reactions? If we want to compare the extent to which different reactions will proceed (which is what chemistry is all about!) why dont we compare easier quantities such as reaction yield? The answer is the following. If you are told that reaction 1 has an equilibrium yield of 40% and reaction 2 has an equilibrium yield of 60%, which reaction has the greater tendency to proceed? We cannot tell since we have not been told the all the concentrations and we know that any reaction can be made to go forwards or backwards by changing the concentrations. To compare the reactivities of different reactions fairly, we need to compare reactions at the same concentrations (lets choose standard state concentrations). This is exactly what Go values do. A more negative value of Go corresponds to a more reactive reaction.
Uses of the vant Hoff equation

We can derive how equilibrium constants vary with absolute temperature T as follows. We know:
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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

and

G o = RT ln K G o = H o TS o

where Ho and So are the values of H and S when all species are in their standard states. Hence RT ln K = H o TS o RT ln K = H o TS o RT ln K = H o + TS o ln K = H o S o + RT R

Finally

If we measure a series of K values at different absolute temperatures, then a plot of lnK as the Y axis (called the ordinate) versus (1/T) as the X axis (called the abscissa) will give a straight line graph with Graph slope = -(Ho/R) Intercept on the Y axis = (So/R)
temperature/ C 0 10 20 30 40 50
o

K 0.5 1.1 2 3.9 8.4 17

T/K 273.15 283.15 293.15 303.15 313.15 323.15

(1/T)/K 0.003661 0.003532 0.003411 0.003299 0.003193 0.003095

-1

lnK -0.693147 0.09531 0.693147 1.360977 2.128232 2.833213

4 3 lnK 2 1 0 -1 0.003 0.0032 0.0034 (1/T)/K-1 0.0036 0.0038 y = -6144x + 21.745

From the graph, the slope = -6144 K (N.B. remember to include both the sign and the units!) Ho = -slope x R = -(-6144 x 8.314) = +51081 J mol-1 Ho = +51.1 kJ mol-1 From the graph, we get that the intercept on the Y axis = 21.745 = (So/R). Hence So = intercept x R = 21.745 x 8.314 = 180.8 J mol-1 K-1 So = 180.8 J mol-1 K-1 Page 17 of 17
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

This example shows how we can separate the total Gibbs free energy driving force for this reaction into the contributions coming from bond making/bond breaking (i.e. the enthalpy change) and from order/disorder (i.e. TSo). For this example, K increases with increasing temperature which means the reaction is endothermic, i.e. Ho is positive and disfavours the reaction. The standard entropy change is positive which means the products are more disordered than the reactants. The entropy change is driving the reaction forward against an unfavourable enthalpy change. In many exam questions, you will not be asked to plot a graph. Instead you will be given only two values of K (lets call them K1 and K2) at two values of T (T1 and T2). In the following example, we will use two values from the data table and graph shown above. Obviously, we should get roughly the same final answers (not exactly since the example graph data has some scatter due to uncertainties). We choose and K1 = 0.5 at T1 = 273.15 K2 = 17 at T1 = 323.15

We apply our basic equation to both sets of values as follows ln K1 = H o S o + RT1 R

ln K 2 =

H o S o + RT2 R

Looking at these two equations, we can see that we can get rid of So/R (a constant in both equations) by subtracting one equation from the other. ln K1 ln K 2 = Some re-arranging gives K1 H o ln = K R 2 Put in the numbers
H o 1 1 0 .5 ln = 8.314 273.15 323.15 17

H o H o + RT1 RT2

1 1 T T 2 1

Hence, Ho = 51.8 kJ mol-1 (as expected, this agrees roughly with our previous answer) To calculate the So, we can take one value of K and work out Go. We will take the value at T = 273.15 K (although we could take either value and still get the same answer). Page 18 of 18
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

At T = 273.15, K = 0.5 and Go = -RTlnK = -(8.314 x 273.15) x ln(0.5) Go = +1574 J mol-1 = Ho - TSo = 51800 273.15 x So Hence So = -(1573 51800)/273.15 = +184 J mol-1 K-1 So = +184 J mol-1 K-1 (again, this roughly agrees with our previous answer) More general exam question tips. If asked to quote an equation, take care to properly define all the terms. If asked to plot a graph, take care to label all axes properly with their units When starting a calculation, try to think in advance on any calculation: will the answer will positive or negative? roughly how big is the answer? what are the units of the answer?
Tabulated values of So and Ho can be used to calculate equilibrium constants

We have seen that define Ho values for stable elements as zero enables us to obtain Ho values for compounds. It is also true that So for perfect crystals at 0 K will be zero because they will be perfectly ordered under these conditions and hence have zero disorder or entropy. Using this fact with additional equations from thermodynamics and measured quantities, So values can be derived for any compound at any temperature and pressure. Tabulated values of So and Ho can then be used to calculate equilibrium constants as shown in the example below. Question. Find the equilibrium constant for the reaction, at 25oC 0.5N2(g) + 0.5(O2(g) NO(g) given that Ho at 298.15 K is 89.9 kJ mol-1 for the reaction and the standard molar entropies at 298.15 K of NO, O2 and N2 are 210, 205 and 192 J mol-1 K-1 respectively. Answer. We first calculate So So = So for NO (0.5So for O2 + 0.5So for N2) So = 210 102.5 96 So = 11.5 J mol-1 K-1 Hence Go = Ho TSo = 89900 (289.15 x 11.5) = 86471 J mol-1 G o From G o = RT ln K we get that K = exp RT

K = 6.9 x 10-16 Putting in numbers gives This is a very small number which tells us that the equilibrium product concentrations are very much less that the equilibrium reactant concentrations. In fact, this equilibrium constant is so low that it is very hard to measure. Thermodynamics is enabling us to use other measurements to calculate equilibrium constants which we cannot measure.

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

Page 20 of 20
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

Some final points about standard states. We have focussed on species in solution for which the usual standard state is 1 M. Other concentration scales can be used. For example, the standard state can be taken to be unit mole fraction, i.e. the pure material. For gases where the concentration is proportional to pressure, common standard states are either unit pressure or unit concentration. For solids or immiscible liquids (where the concentration is fixed by the density) the standard state is usually taken to be the pure solid.
Chemical Kinetics

Equilibrium thermodynamics tells us about the extent to which reactions will proceed if allowed infinite time. Chemical kinetics tells us about how fast reactions proceed towards their equilibrium state. We first need to define some key terms.
Reaction rate is the rate of change of concentration with respect to time. It is helpful to consider plots of concentration versus time for a simple reaction. We will consider the reaction

A B Mathematically, the reaction rate =

d [A] d [B ] =+ The rate is a differential quantity dt dt which is equal to the negative slope of the tangent of a plot of concentration of A versus time or to the positive slope of a plot of concentration of B versus t. Obviously, the rate cannot be negative which is why the minus sign must be in front of the negative slope d[A]/dt but not in front of the positive slope d[B]/dt. Because one molecule of B is formed for every molecule of A lost, it is clear that the plot of [B] versus time must be an exact mirror image of the plot of [A] versus time.

For a more complicated reaction stoichiometry, such as A + 2B + 3C 2X + Y + Z

rate =

d [A] 1 d [B ] 1 d [C ] 1 d [X ] d [Y ] d [Z ] = = =+ =+ =+ dt 2 dt 3 dt 2 dt dt dt

The normal units of rate are M s-1.

The Rate Law

Reaction rates generally depend on the concentrations of one or more of the different reactants of the reaction in a way that depends on the mechanism of the reaction. The relationship between rate and all the reactant concentrations is called the rate law for that particular reaction and must be measured experimentally. Consider a general reaction A + B + C + products

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

The rate law always has the general form Rate = k [A]a [B]b [C]c. where and so on

k is the rate constant. This is what the rate would be if the concentrations of all the reactants were all equal to unity. [species] is the time-dependent concentration of a species The superscript a, b, and c are the ORDERS with respect to the species A, B and C. Chemical reaction orders are generally either 0, 1 or 2 but there are a few exceptions. The overall order of a chemical reaction is the sum of all the orders with respect to the individual species.

The units of a rate constant depend on the overall order of the reaction rate law. As usual, the units of k for rate laws with different overall orders can be worked out by recognising that the units of the LHS of an equation must equal the units of the RHS. This is shown in the table below for a general rate law of the form Rate = k [X]n Overall order n 0 1 2 3 n Units of rate M s-1 M s-1 M s-1 M s-1 M s-1 Units of k M s-1 s-1 M-1 s-1 M-2 s-1 M-(n-1) s-1 Units of [X]n No units M M2 M3 Mn

Note that you can only compare rate constants with the same overall order and hence the same units. It is obviously nonsense to say something like the first-order rate constant of 10 s-1 is larger than the second-order rate constant of 3 M-1 s-1. This is like saying that 10 kg is larger than 2 m.
How to derive the equation for concentration versus time from the rate law

A rate law is a differential equation since it involves the rate which is a differential quantity. We can obtain the equation for how the reactant concentration depends on time (which is normally what is measured in a kinetics experiment) by integration of the rate law. We shall show this for zero, first and second-order rate laws. Zero order rate law For a reaction A products

For which the rate law is measured to be -d[A]/dt = k [A]0 = k since any quantity raised to the power zero is simply equal to 1. We proceed by rearranging the equation so that all concentration terms are on the LHS and everything else is on the RHS. Both sides are then integrated (see sheet list all the simple Page 22 of 22
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

integrals which you need to know) and the constant of integration is added to the RHS.

d [A] = kdt
[A] = -kt + constant of integration We find the constant by noting that [A] = [A]o (the initial concentration of A) when t = 0. Hence the constant of integration is equal to [A]o. The final integrated rate equation is then:
[A] = [A]o kt

We can see from this result that, if the kinetics are zero order, a plot of [A] (as ordinate versus t as abscissa will be linear with slope equal to k and intercept on the ordinate equal to [A]o.
k/M s-1 0.002 [A]o/M 0.3

ZERO ORDER KINETICS time/s [A]/M 0 0.3 10 0.28 0.3 20 0.26 30 0.24 0.2 40 0.22 50 0.2 60 0.18 0.1 70 0.16 80 0.14 0 90 0.12 0 100 0.1 110 0.08 120 0.06 130 0.04 140 0.02 150 0 160 -0.02 concentration/M

50

time/s

100

150

First order rate law

For a reaction

A products

For which the rate law is measured to be -d[A]/dt = k [A]1 = k [A]

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

We again proceed by re-arranging the equation so that all concentration terms are on the LHS and everything else is on the RHS. Both sides are then integrated (see sheet list all the simple integrals which you need to know) and the constant of integration is added to the RHS.

[A]

d [A]

= kdt

ln[A] = -kt + constant of integration We find the constant by noting that [A] = [A]o (the initial concentration of A) when t = 0. Hence the constant of integration is equal to ln[A]o. The final integrated rate equation is then: ln[A] = ln[A]o kt which can also be written as
[A] = [A]oexp(-kt)

We can see from this result that if the kinetics are first order, a plot of ln[A] (as ordinate versus t as abscissa will be linear with slope equal to k and intercept on the ordinate equal to ln[A]o.
k/s-1 0.03 [A]o/M 0.3 concentration/M

0.3 ln([A]/M)
-1.203972804 -1.503972804 -1.803972804 -2.103972804 -2.403972804 -2.703972804 -3.003972804 -3.303972804 -3.603972804 -3.903972804 -4.203972804 -4.503972804 -4.803972804 -5.103972804 -5.403972804 -5.703972804 -6.003972804

FIRST ORDER KINETICS time/s [A]/M [B]/M 0 0.3 0 10 0.22225 0.077754534 20 0.16464 0.135356509 30 0.12197 0.178029102 40 0.09036 0.209641736 50 0.06694 0.233060952 60 0.04959 0.250410334 70 0.03674 0.263263072 80 0.02722 0.272784614 90 0.02016 0.279838346 100 0.01494 0.285063879 110 0.01106 0.28893505 120 0.0082 0.291802883 130 0.00607 0.293927427 140 0.0045 0.295501327 150 0.00333 0.296667301 160 0.00247 0.297531076

0.2 0.1 0 0 50 time/s 100

[A] [B]

150

0 -1 -2 -3 -4 -5 -6 -7 0

ln(concentration/M)

y = -0.03000x - 1.20397 50 100 time/s 150

It is a particular feature of first-order reactions that the half-life (equal to the time taken for the concentration to halve) is the same which ever concentration you start from (see graph below). It takes exactly the same time to go from 1 M to 0.5 M as it does to go from 0.0001 M to 0.00005 M. For a first-order reaction the half-life is equal to (ln2/k) which you can see does not depend on the concentration. For all other order reactions, the half-life does depend on the initial concentration. Try Page 24 of 24
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

drawing in the 1st, 2nd, 3rd, etc. half-lives on the zero- and second-order concentration versus time plots to demonstrate that this is the case.
0.3

concentration/M

0.2

0.1

0 0 50 time/s 100 150

You can see from this graph showing the 1st, 2nd, 3rd, etc. half-lives for a first-order reaction that there is no time when the reaction is complete. Each new half -life only halves the concentration remaining. Zero concentration is never reached.
There are two types of second order rate law

Type 1. For a reaction

A products

For which the rate law is measured to be -d[A]/dt = k [A]2 We again proceed by re-arranging the equation so that all concentration terms are on the LHS and everything else is on the RHS. Both sides are then integrated (see sheet list all the simple integrals which you need to know) and the constant of integration is added to the RHS.

[A]

d [A]
2

= kdt

1/[A] = kt + constant of integration We find the constant by noting that [A] = [A]o (the initial concentration of A) when t = 0. Hence the constant of integration is equal to 1/[A]o. The final integrated rate equation is then:
1/[A] = 1/[A]o + kt

We can see from this result that if the kinetics are first order, a plot of 1/[A] (as ordinate versus t as abscissa will be linear with slope equal to k and intercept on the ordinate equal to 1/[A]o. Page 25 of 25
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

k/M-1s-1 0.3

SECOND ORDER KINETICS (1/[A])/M-1 time/s [A]/M 0 0.3 3.333333333 10 0.15789 6.333333333 20 0.10714 9.333333333 30 0.08108 12.33333333 40 0.06522 15.33333333 50 0.05455 18.33333333 60 0.04688 21.33333333 70 0.0411 24.33333333 80 0.03659 27.33333333 90 0.03297 30.33333333 100 0.03 33.33333333 110 0.02752 36.33333333 120 0.02542 39.33333333 130 0.02362 42.33333333 140 0.02206 45.33333333 150 0.02069 48.33333333 160 0.01948 51.33333333

concentration/M

[A]o/M 0.3

0.3 0.2 0.1 0 0 50 time/s 100 150

60 (1/concentration)/M-1 50 40 30 20 10 0 0 50 100 time/s 150 y = 0.30000x + 3.33333

Type 2. For a reaction

A +B products

For which the rate law is measured to be -d[A]/dt = k [A]1 [B]1 This equation is harder to integrate and we will simply quote the final answer. (See for example P.W. Atkins, 7th edition, page 875 for the maths)
kt = [B ][A]0 1 ln [B]0 [A]0 [A][B]0

This type of second-order reaction (overall second order but first order with respect to two different reactants) is the most common type. What does a 2nd order rate constant tell us? For a 2nd order reaction A + A products which is second order in A, then the half-life t1/2 (which does depend on the initial concentration) is
t1 / 2 =
1 k [A]0

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

The first half-life (i.e. the time to go from [A]o to [A]o/2) depends on both the rate constant k and the initial concentration [A]o. The table below shows some values which help to relate k, concentration and t1/2 which provides a measure of the time taken by a reaction to reach a know amount of conversion to products.
k/M-1 s-1 1 1 [A]o/M 1 10-3 10-6 10-3 Half-life/s 1 1000 1000000 1000000000 Comments

10-6 103 106 1010

10-3 10-3 10-3

About quarter of an hour About a fortnight About 30 years, too slow to measure kinetics as research projects usually only last 3 years! Fastest possible (diffusion controlled) value of k in water at room temperature. The half-life is 100 ns. For comparison, light travels approximately 100 ft in 100 ns

1 10-3 10-7

Reactions cannot go infinitely fast, i.e there is a maximum value of the rate constant k. For 2nd order reactions involving two solute molecules reacting together in a solvent, the maximum rate is controlled by the speed at which the molecules can diffuse together. For water as solvent at room temperature, the maximum, diffusion controlled rate constant is approximately 1010 M-1 s-1. There are also maximum values for different types of reactions. As you can see from the table, you need to be able to measure reaction kinetics in ns in order to measure the fastest possible 2nd order rate constants with mM concentrations. See your Physical Chemistry text for a description of some of the special fast techniques used to do this.
Reactions with a significant backwards rate which approach equilibrium

So far, we have considered reactions which proceed virtually to completion. What happens if a reaction proceeds to an equilibrium position corresponding to only partial conversion to products? We have to consider both the forward and reverse rates as seen for the example reaction below. A+B C with forward rate constant kf (2nd order) and reverse rate constant kr (1st order). The rate law now has to consider both the forward and reverse rates which depend on both the reactant and product concentrations as show below. rate = -d[A]/dt = -d[B]/dt = +d[C]/dt = {kf [A] [B] kr [C]} This rate law can be integrated in the usual way but is more involved (consult a more text for more details). As equilibrium is reached, the forward rate (= kf [A] [B]) decreases as the concentrations of A and B decrease whereas the reverse rate (= kr [C]) increases as the product concentration increases. Equilibrium is reached when Page 27 of 27
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

the overall rate is zero which happens when the forward rate is balanced by the reverse rate. Reactions do not stop at equilibrium; they simply proceed equally fast in both the forward and reverse directions. At equilibrium Hence Re-arranging gives rate = 0 ={kf [A] [B] kr [C]} kf [A] [B] = kr [C]

kf kr

[C ] =K [ A][ B]

(K is the equilibrium constant)

Show for yourself that this analysis works for reactions with any numbers of reactant and product species. For any reaction, the equilibrium constant is always equal to the forward rate constant divided by the reverse rate constant.
Effect of temperature on reaction rate constants

Svante Arrhenius first described the relationship between k (any order) and absolute temperature T. It can be written in two equivalent ways as shown below. lnk = lnA Ea/RT or where k = A exp(-Ea/RT) A is a constant called the pre-exponential factor Ea is the activation energy equal to the difference in enthalpy between the reactants and the highest enthalpy point of the reaction profile. R is the gas constant

Note that the Arrhenius equation has the same form as the vant Hoff equation describing how an equilibrium constant varies with temperature. This can be seen by comparing your notes for K with those below. If we measure a series of k values at different absolute temperatures, then a plot of lnk as the Y axis (called the ordinate) versus (1/T) as the X axis (called the abscissa) will give a straight line graph with Graph slope = -(a/R) Intercept on the Y axis = lnA

Page 28 of 28
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

temperature/ C 0 10 20 30 40 50

k/s 0.5 1.1 2 3.9 8.4 17

-1

T/K 273.15 283.15 293.15 303.15 313.15 323.15

(1/T)/K 0.003661 0.003532 0.003411 0.003299 0.003193 0.003095

-1

ln(k/s ) -0.693147 0.09531 0.693147 1.360977 2.128232 2.833213

-1

4 3 ln(k/s ) 2 1 0 -1 0.003 0.0032 0.0034 0.0036 0.0038 (1/T)/K-1

-1

y = -6144x + 21.745

From the graph, the slope = -6144 K (N.B. remember to include both the sign and the units!) a = -slope x R = -(-6144 x 8.314) = +51081 J mol-1 Ea = +51.1 kJ mol-1 As we shall see, the activation energy Ea is always positive. This means that rate constants (and hence rates at fixed concentrations) always increase with increasing temperature. As you can see from the table above, an activation energy of about 50 kJ mol-1 corresponds to the rate constant approximately doubling every 10oC or so. An activation energy of about 100 kJ mol-1 corresponds to the rate constant approximately doubling every 5oC or so. An activation energy of zero means that the rate constant will not vary with temperature. In many exam questions, you will not be asked to plot a graph. Instead you will be given only two values of k (lets call them k1 and k2) at two values of T (T1 and T2). In the following example, we will use two values from the data table and graph shown above. Obviously, we should get roughly the same final answers (not exactly since the example graph data has some scatter due to uncertainties and taking the best slope gives an averaging effect). We choose and k1 = 0.5 at T1 = 273.15 k2 = 17 at T1 = 323.15

We apply our basic equation to both sets of values as follows

ln k1 = Ea + ln A RT1

Page 29 of 29
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

ln k 2 =

Ea + ln A RT2

Looking at these two equations, we can see that we can get rid of lnA (a constant in both equations) by subtracting one equation from the other. ln k1 ln k2 = Some re-arranging gives
k1 Ea 1 1 ln k = R T T 2 2 1

Ea E + a RT1 RT2

Put in the numbers

1 E 1 0.5 ln = a 8.314 273.15 323.15 17 Hence, Ea = 51.8 kJ mol-1 (as expected, this agrees roughly with our previous answer) As you can see, the procedure to use the Arrhenius equation is obviously the same as for the vant Hoff equation describing the variation of K with T.
Meaning of Ea and A in the Arrhenius equation

For almost all chemical reactions, some of the bonds of the reactants must be fully or partially broken before they can form the new bonds of the products. This bond breaking costs enthalpy which therefore goes up. The subsequent formation of new bonds releases enthalpy. Hence, as seen below, the enthalpy first increases and then decreases. The difference in enthalpy between the maximum point (this is called the transition state of the reaction) and the reactants is the activation energy.

Transition state Activation energy reactants

0 0 reaction co-ordinate

reaction enthalpy

products

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

How big do we expect activation energies to be? From the diagram above, we can see that Ea is the energy needed to partially break the chemical bonds which must be broken to form the reaction products. We know that the energy need to fully break a mole of chemical bonds (the usual bond energy) is generally in the range 200-500 kJ mol-1 (The C-C bond energy is 440 kJ mol-1). Because reactive bonds will be relatively weak and we only need to partially break them before the new bonds start to form, activation energies of 0-200 kJ mol-1 seem intuitively reasonable.

Molecules have a distribution of thermal energies around the average energy equal to RT for one mole of molecules at absolute temperature T. At any time during a reaction, a particular molecule (or set of molecules) will only react if their thermal energy from a collision with neighbours is equal to or greater than the energy barrier to the reaction which is the activation energy. As derived by Boltzmann, the fraction of molecules having an energy grater than or equal to Ea is fraction = exp(-Ea/RT) We can recognise this equation as the exponential part of the Arrhenius equation. It explains why reactions are slow when either the temperature is low or the activation energy is high. Under these conditions, only a very small fraction of the molecular collisions going on all continuously have enough energy to react. Hence we have to wait a long time before a rare collision with enough energy for reaction occurs. The table below shows how this fraction changes with Ea and T.
Ea/kJ mol1

T/K

50 50 50 0 20 50 100 200

300 (room temp) 1000 10000 300 300 300 300 300

Fraction of molecules with energy Ea or greater 2.0 x 10-9 2.4 x 10-3 5.5 x 10-1 1 3.3 x 10-4 2.0 x 10-9 3.9 x 10-18 21.5 x 10-35

Successful collisions resulting in reaction 1 in 500,000,000 1 in 400 1 in 2 All of them 1 in 3000 1 in 500,000,000 1 in 2.6 x 1017 1 in 6.7 x 1034

For typical temperatures and activation energies, the fraction of collisions which is successful is rather small. Obviously, when the activation energy is zero, all collisions are successful. This can be the case for reactions of free radicals for which no bonds have to be broken before news bonds can form. The fraction of collisions which are successful can also reach unity when the absolute temperature is infinitely large. Inspection of the Arrhenius equation shows that, when either Ea = 0 or T = , then the exponential part becomes equal to 1 and the rate constant k becomes equal to the pre-exponential factor A. This then tells us the meaning of A in the Arrhenius equation. A is what the rate constant would be if all collisions had enough energy to react, i.e. if either Ea = 0 or T = .
Activation energies for reversible reactions

We saw earlier that measuring the forward and reverse rate constants for a reversible reaction enables us to work out the equilibrium constant. In a similar way, measuring Page 31 of 31
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

the activation energies for both the forward and reverse reactions of a reversible reaction enables us to calculate the equilibrium value of H for the reaction. This can be seen in the diagram below. Ea (forward)

reaction enthalpy

Ea (reverse) Equilibrium H
0 0 reaction co-ordinate

Catalysis

Catalysis is the process whereby a reaction rate is increased by a catalyst. Catalysts : are not consumed in the reaction increase the rates of both the forward and reverse reactions do not change equilibrium constants Catalysts work by binding with (and hence lowering the energy of) reaction intermediates including the transition state. Because the energy of the transition state is this reduced relative to the original (unbound) reactants or products, the activation energy is reduced and the reaction rate is increased for both the forward and reverse. The catalyst does alter the energies of the unbound reactant and products and hence the overall equilibrium constant of the reaction is not affected by the catalyst. This is shown schematically in the energy diagram below.
uncatalysed catalysed

reaction energy 0 0 reaction co-ordinate

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

Spectroscopy

We will cover here only the basic concepts of spectroscopy. Fundamentally, spectroscopy tells us about the amount of light absorbed and the energy level differences in atoms or molecules. This information can be used to identify unknown molecules, estimate concentrations and determine molecular properties such as bond lengths and bond strengths with very good precision. There are many different forms of spectroscopy but most spectrometers have the following common features. Light source emitting a range of wavelengths Monochromator to select a single wavelength Sample Light detector

The light source produces a range of wavelengths, e.g. a normal light bulb emitting in the visible region emits wavelengths from about 400-700 nm. The monochromator enables the selection of light of a single wavelength which is then incident onto the sample. Within the sample, some fraction of the light might be absorbed by the sample whereas the remainder is transmitted through the sample and detected by the detector. In general, light is absorbed by the sample if the difference between two energy levels in the sample matches the energy of the light (which corresponds to the wavelength, frequency or colour of the light). The transmitted light intensity is measured as a function of the light energy (expressed appropriately) which produces a spectrum of the sample. Spectra can expressed in various ways for both the ordinate (which might be expressed as transmitted light intensity or absorbance) and the abscissa (which might be wavelength, frequency, energy or wavenumbers). The diagram below shows a schematic spectrum as a plot of transmitted light intensity versus light energy. The light energy values when the transmitted intensity dips below the light intensity which is incident on the sample (= I0, shown as the horizontal dashed line) correspond to the absorption bands of the sample.

transmitted light intensity

light energy

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

The different forms of spectroscopy differ mainly in the type of light used which, in turn, controls the energy range covered in the spectrum and the type of molecular processes which are induced by adsorption of light of that energy. Electromagnetic radiation consists of a wave of oscillating electric and magnetic fields. The wavelength (greek letter lambda) and the frequency (greek letter nu) are related by
= c/

where

= wavelength (units m) c = speed of light (units m s-1) = frequency (units s-1 which are the same as Hz)

Other properties of electromagnetic radiation which it is useful to consider include the following. The period of the wave is equal to 1/ and is the time for one complete oscillation. The wavenumber of a wave is simply the number of waves within a unit length and is equal to 1/. Some spectroscopists use wavenumber as the light energy scale in spectroscopy because the photon energy is proportional to wavenumber (have a go at proving this for yourself). The energy of a single photon = h where h is Plancks constant (h = 6.6 x 10-34 J s). In the context of chemistry, it is useful to consider the energy of one mole of photons which is (obviously) equal to Nh where N is Avogadros number. We can then compare this energy with other chemical energies that we know such as bond energies (e.g. 440 kJ mol-1 for C-C bonds) and thermal kinetic energy (approximately equal to 2.5 kJ mol-1 at room temperature. The table below shows the key properties of different forms of light.
c/ m s-1 3.00E+08 h/J s 6.63E-34 N/mol-1 6.02E+23

type of light X ray X ray X ray X ray vacuum UV vacuum UV UV/vis infrared far infrared microwave microwave microwave radio radio radio radio

wavelength/m 1.00E-12 1.00E-11 1.00E-10 1.00E-09 1.00E-08 1.00E-07 1.00E-06 1.00E-05 1.00E-04 1.00E-03 1.00E-02 1.00E-01 1.00E+00 1.00E+01 1.00E+02 1.00E+03

frequency/s-1 3.00E+20 3.00E+19 3.00E+18 3.00E+17 3.00E+16 3.00E+15 3.00E+14 3.00E+13 3.00E+12 3.00E+11 3.00E+10 3.00E+09 3.00E+08 3.00E+07 3.00E+06 3.00E+05

-1 period/s wavenumber/m 3.34E-21 1.00E+12 3.34E-20 1.00E+11 3.34E-19 1.00E+10 3.34E-18 1.00E+09 3.34E-17 1.00E+08 3.34E-16 1.00E+07 3.34E-15 1.00E+06 3.34E-14 1.00E+05 3.34E-13 1.00E+04 3.34E-12 1.00E+03 3.34E-11 1.00E+02 3.34E-10 1.00E+01 3.34E-09 1.00E+00 3.34E-08 1.00E-01 3.34E-07 1.00E-02 3.34E-06 1.00E-03

energy of 1 photon/J 1.99E-13 1.99E-14 1.99E-15 1.99E-16 1.99E-17 1.99E-18 1.99E-19 1.99E-20 1.99E-21 1.99E-22 1.99E-23 1.99E-24 1.99E-25 1.99E-26 1.99E-27 1.99E-28

energy of 1 mol of photons/kJ mol-1 1.20E+08 1.20E+07 1.20E+06 1.20E+05 1.20E+04 1.20E+03 1.20E+02 1.20E+01 1.20E+00 1.20E-01 1.20E-02 1.20E-03 1.20E-04 1.20E-05 1.20E-06 1.20E-07

molecular process nuclear excitation excitation of inner shell electrons excitation of inner shell electrons excitation of inner shell electrons excitation of outer shell (bonding) electrons excitation of outer shell (bonding) electrons excitation of outer shell (bonding) electrons molecular vibration molecular vibration molecular rotation molecular rotation molecular rotation nuclear spin excitation in a magnetic field nuclear spin excitation in a magnetic field nuclear spin excitation in a magnetic field nuclear spin excitation in a magnetic field

Considering this table, we first discuss the energies of 1 mole of the different photons. We can see that chemical bond energies (100s of kJ mol-1) correspond to UV radiation. It then follows that UV light is used to do photochemistry in which light is used to break chemical bonds. Higher energy X ray photons excite inner orbital electrons (inner electrons are closer to the nucleus and so require a higher energy photon to kick then out) and are therefore used to identify atoms. X ray spectroscopy does not tell us about outermost filled (bonding) orbitals. Page 34 of 34
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

The thermal energy of molecules at room temperature (approx. 2.5 kJ mol-1) corresponds to the far infrared. We can then see that thermal energy is high enough to enable molecular processes of moving, rotation and vibration. It is not enough to excite electrons. Radiowaves are very low energy photons. They have enough energy to flip spinning nuclei (which behave like tiny magnets) in an external magnetic field. This is the basis for nuclear magnetic resonance (NMR). The relative photon energies of X Rays and radiowaves are one reason which NMR scanners are gaining in popular use in hospitals. When you are X rayed in hospital, high energy X ray photons smash through your molecules creating reactive free radicals which can attack your DNA and cause a variety of diseases. In contrast, having an NMR scan exposes you to very low energy photons which cause no permanent molecular changes and is safe. In the table, it is also interesting to look down the column showing the period of the wave. When absorption occurs, the light period corresponds to the timescale of the molecular process occurring as a result of light absorption. For example, microwave absorption in liquid water tells us that a water molecule takes about 8 ps to rotate in liquid water at room temperature. Electronic transitions of outer shell electrons take some fs. Consult your physical chemistry textbook to learn more details of spectroscopy. Check that you can use the equations above correctly by calculating a few of the different entries in the table for yourself.

Absorbance and concentration the Beer Lambert Law

We know from everyday experience that the amount of light absorbed by a solution of an absorbing solute depends on its concentration. Using measurements of the light absorbed to determine concentration is a very useful aspect of spectroscopy, particularly UV/visible spectroscopy. We consider the absorption of monochromatic (= single wavelength) light by a solute of concentration c contained within a cell of path length l. Sample path length = l

Incident light intensity = I0

Transmitted light intensity = I The light intensity decreases exponentially from I0 to I as the light beam passes through the sample

The concentration of the absorbing species is proportional to the absorbance A (NOT to the transmitted light intensity). The absorbance A is defined in terms of the measured incident and transmitted light intensities as Page 35 of 35
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

A = log10(I0/I) Absorbance has no units. Use the table below to understand what the different absorbance values mean.
absorbance 0 1 2 3 4 % of incident light absorbed 0 90 99 99.9 99.99 % of incident light transmitted 100 10 1 0.1 0.01

For particular wavelength of light and a particular absorbing solute, the absorbance is proportional to both the sample path length and the solute concentration. This is shown in the Beer-Lambert Law. A = log10(I0/I) = c l where A is the absorbance measured in a spectrometer (unitless) is the extinction coefficient for the particular solute at that wavelength. Units = M-1 cm-1 c is the solute concentration in M units l is the sample path length in cm units.

Question. The extinction coefficient of a protein is 2.53 x 106 M-1cm-1 at a wavelength of 280 nm. The absorbance at 280 nm of an unknown solution of the protein is 1.342 in a 5 mm path length cell. What is the protein solution concentration? Answer. We know that A = log10(I0/I) = c l Hence c = A/ l = 1.342/(2.53 x 106 x 0.5) Note that we have converted the path length units from mm to cm so that they cancel with the cm units in the extinction coefficient. To avoid mistakes in your calculations, always check when you enter numbers in an equation that the units of the LHS and RHS match as they should.

Hence

Protein concentration = 1.061 x 10-6 M

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

Basic Physical Chemistry. (Part of module 06512 Foundations of Chemistry 2) Practice questions General

1.

Calculate the following unit conversions volume = 1 cm3 = ? m3 volume = 1 cm3 = ? nm3 density = 1 g cm-3 = ? kg m-3 (pressure x volume) is an energy. 1 dm3 atm = ? J

Inter-molecular forces

2.

Estimate the average separation between water molecules in liquid water. Hint. Imagine each water molecule exactly fills a cube. Take the side length of the cube to be approximately equal to the average separation. [Avogadros number = 6.02 x 1023 mol-1, RMM of water = 18 g, density of water = 1.00 g cm-3] For each of the molecules below, state whether they have a non-zero permanent dipole moment and whether their polarisability will be low or high benzene nitrobenzene cyclohexane chlorocyclohexane para-dichlorobenzene ortho-dichlorobenzene

3.

Ideal gases

4.

Re-arrange the ideal gas equation to obtain an equation for the concentration of an ideal gas. Use your equation to calculate the concentration in units of M of an ideal gas at 298 K and pressure of 560 Pa. [Gas constant R = 8.314 J mol-1 K-1] Calculate the pressure when 0.5 g of nitrogen and 1 g of oxygen are sealed in a container of volume equal to 10 litres at 25oC. [Gas constant R = 8.314 J mol-1 K-1]

5.

Equilibrium constants and thermodynamics

6.

A reaction A B is found to have an equilibrium yield of 50% at 25oC and 75% at 42oC. Calculate Ho for the reaction. [Gas constant R = 8.314 J mol-1 K-1] Hint. First calculate K at each temperature and then use the vant Hoff equation. Before you start calculating, estimate first whether you expect Ho to be positive or negative.

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

7.

A reaction has an equilibrium constant equal to 1.7 x 104 at 30oC and 1.3 x 103 at 70oC. Calculate Ho and So for the reaction. Is the reaction driven by enthalpy or entropy? [Gas constant R = 8.314 J mol-1 K-1]

Reaction kinetics

8.

The rate of a reaction is measured at different concentrations of one of the reactants (species A) whilst keeping all other concentrations and the temperature constant. The rate is 0.0012 M s-1 when [A] = 0.15 M and 0.00037 when [A] = 0.083 M. What is the order of the reaction with respect to the species A? A first order reaction has a rate constant of 0.23 s-1. Calculate the half-life. The reaction is started with and initial reactant concentration of 0.1 M. Calculate the concentration remaining after 25 s. A reaction has a rate constant of 7 M-1 s-1 at 25oC and an activation energy of 72 kJ mol-1. What is the overall order of the reaction? Calculate the temperature required to increase the rate constant to 43 M-1 s-1. [Gas constant R = 8.314 J mol-1 K-1]

9.

10.

Spectroscopy

11.

An electronic transition in a molecule has an energy of 357 kJ mol-1. Calculate the wavelength, wavenumber, frequency and period of the electromagnetic radiation corresponding to this energy. What type of light is this? [Avogadros number = 6.02 x 1023 mol-1, Plancks constant = 6.626 x 10-34 Js, speed of light = 2.998 x 108 m s-1] A dye has an extinction coefficient of 4500 M-1 cm-1 at a wavelength of 476 nm. A solution of the dye (in a non-absorbing solvent) in a 10 cm path length cell is found to transmit 48% of the incident light. Calculate the concentration of the dye.

12.

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

Answers

1.

volume = 1 cm3 = 1 x 10-6 m3 volume = 1 cm3 = 1 x 1021 nm3 density = 1 g cm-3 = 1000 kg m-3 (pressure x volume) is an energy. 1 dm3 atm = 101.325 J Mass of 1 mole = 18 g. Hence, volume of 1 molecule = 18 x 10-6/6.02 x 1023 = 3 x 10-29 m3 The average separation is equal to the cube root of the volume = 3.1 x 10-10 m Average separation = 0.31 nm
molecule non-zero dipole moment ? Benzene no Nitrobenzene yes Cyclohexane no Chlorocyclohexane yes para-dichlorobenzene no (cancels) ortho-dichlorobenzene yes polarisability? high (aromatic) high low (non aromatic) low high high

2.

3.

4.

PV = nRT and concentration = (n/V) Hence concentration (n/V) = R/(RT) Concentration = 560/(298 x 8.314) = 0.226 mol m-3 Concentration = 2.26 x 10-4 M moles nitrogen = 0.5/28 = 0.01786 mol moles oxygen = 1/32 = 0.03125 mol total moles n = 0.04911 mol P = nRT/V = 0.04911 x 8.314 x 298.15/(10 x 10-3) (converted litres to m3) Pressure = 1.217 x 104 Pa Because the equilibrium yield of product increases with increasing temperature, we know the reaction is endothermic and Ho is positive. From the yields, K = 1 at 25oC and K = 3 at 42oC. Putting these numbers into the vant Hoff equation gives the answer.
K1 H o ln = K R 2 1 1 T T 2 1

5.

6.

Ho = +50.49 kJ mol-1

7.

We first note that K decreases with increasing temperature which tells us that this reaction is exothermic, i.e. Ho is negative. At 30oC, Go = -RTlnK = -8.314 x 303.15 x ln(1.7 x 104) = -24551 J mol-1 At 70oC, Go = -RTlnK = -8.314 x 343.15 x ln(1.3 x 103) = -20556 J mol-1 Using the equation Go = Ho TSo, we do the usual procedure when we have two sets of values (i.e. subtract one equation from the other to cancel Ho in this case). -24551-(-20556) = -3995 = -(303.15 343.15)So = +40 x So Page 39 of 39
Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull

Hence So = -99.8 J mol-1 K-1 (this negative entropy change disfavours the reaction) Using this So value and one of our Go values gives us Ho = -54.8 kJ mol-1 Note that the enthalpy change is negative, as expected. K1 H o 1 1 Note also, that you could have used ln = K to calculate R 2 T1 T2 the enthalpy change first and then get the entropy change. This procedure should, of course, give the same answer. 8. We have two values of rate at two values of [A] and so we can write rate1 = k [A]1n rate2 = k [A]2n Dividing one equation by the other and taking logs of both sides then cancels the rate constant k log(rate1/rate2) = n log{[A]1/[A]2} Hence n = log(0.0012/0.00037)/log(0.15/0.083) = 2.0 Order = 2 For a first order reaction the half-life = ln(2)/k which is equal to 3.01 s for this reaction. To calculate the concentration remaining, we use the integrated rate equation [A] = [A]oexp(-kt). Putting in numbers gives Remaining concentration = 3.18 x 10-4 M The rate constant has second order units which tells us that the reaction is overall 2nd order. To calculate the temperature, we use the form of the Arrhenius equation appropriate for two sets of values. k1 Ea 1 1 ln k = R T T 2 2 1 Putting in numbers gives T2 = 318 K which corresponds to Temperature = 44.9oC Energy of 1 mole of photons = Nh = 357000 J mol-1. Hence frequency = 8.949 x 1014 Hz period = 1.117 x 10-15 s = 1.117 fs wavelength = 3.350 x 10-7 m = 335 nm wavenumber = 2.985 x 106 m-1 This is UV light. Because 357 kJ mol-1 corresponds to a typical bond energy, UV light has sufficient energy to break chemical bonds and is therefore used for photochemistry. The absorbance A = log10(I0/I) = log(100/48) = 0.319. Using the BeerLambert law gives Concentration = A/( l) = 0.319/(4500 x 10) = 7.09 x 10-6 M Concentration = 7.09 x 10-6 M

9.

10.

11.

12.

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Basic Physical Chemistry by Paul D.I. Fletcher, Department of Chemistry, University of Hull