Thermodynamics The driving force behind chemical reactions Heat and work ways that a chemical system can

exchange energy with environment 1. capacity to do work (w) work done = force x distance 2. capacity to transfer heat (q) both measured in joules Heat: process of transfer of thermal energy between bodies of diff temperatures. Universe = system + surroundings Open system exchanges matter and energy with surroundings Closed only exchanges energy with surroundings Isolated cannot exchange either Adiabatic only exchanges work Internal energy, U sum of all energies (potential and kinetic) for all particles in the system Kinetic due to motion movement of atoms, molecules, ions (vibration/translation/rotation) Potential depends on position of objects Change in internal energy U= U(final) U(initial) If change is positive, system gains If change is negative, system loses energy change system = - change surroundings First Law of Thermodynamics Energy is not created or destroyed, just transformed Change in internal energy = q + w (q heat added to system, >0) (w work done on system, w>0) Positive work/heat increases energy of system Work in thermodynamics pV work associated with contraction and expansion of gas w = - pexternal x V remember for exam!! Heat in thermodynamics - transfer of thermal energy between 2 bodies of systems due to diff in temperature a means of energy transfer q = CT determined by calorimetry C=heat capacity, T=change in temp Internal energy changes at constant volume rU = qv r = heat of reaction at constant volume

Enthalpy Most reactions occur under constant pressure U = q + w for constant pressure, U = qp - p V qp = U + p V Enthalpy H = U + pV so at constant pressure, H = qp H is heat of reaction at constant pressure Heat change of reaction is enthalpy products enthalpy reactants Internal energy and enthalpy H = U + (pV) Enthalpy is an extensive property if twice as many moles, twice as much heat, double the enthalpy Enthalpy change of the reverse reaction is same magnitude, opposite sign Enthalpy change for a reaction depends on the STATE OF MATTER of reactants and products (different for liquids/gases) Hesss Law Enthalpy change for a reaction dependent only on the energy states of reactants and products and independent of path/number of steps taken. conservation of energy Enthalpy change rH = Hfinal Hinitial = Hproducts Hreactants H and U are state functions final state independent of path taken from start (S and G also) Work and heat are DEPENDENT on the way in which a change of state has occurred therefore not state functions Standard Enthalpy of Reaction heat given out/taken in, at constant pressure Standard state indicated by plimsoll symbol rH Standard state most stable form at particular pressure and temperature, for compoundsL - gases: pressure of 105 Pa - liquids and gases: pure substance - aqueous solutions: concentration is 1 mol/L Standard Enthalpy of Formation fH Change in enthalpy that results from the formation of 1 mole of a compound from its elements at 100 kPa and specified temperature, with all substances in standard states Can do this for reactions which dont actually exist/occur fH for an element in its standard state is 0 Using this to find rH Take reactants apart to their constituent elements

Form products from the elements

Hesss Law and Standard Enthalpies Implies can find H for AC as a sum of those for AB, BC Includes converting all reactants elements products Enthalpy change for converting elements into a given substance is the standard enthalpy of formation fH for that substance Can use Hesss Law to calculate rH for many reactions using tabulated enthalpies Standard Enthalpies (or heats) of Formation fH = enthalpy change associated with formation of 1 mole of a substance from its elements But its value depends on conditions eg. pressure, allotropes Diagrammatic view of Hesss Law

Standard enthalpy change example 4NH3 + 7O2 4NO2 + 6H2O fH = [4x fH(NO2) + 6x fH(H20)] [4x fH(NH3) + 7x fH(O2)]

(ie. products reactants) If you reverse a reaction, change the sign of H If you multiply a coefficient, multiply H by the same coefficient (H is extensive depends on amount of substance present [intensive is independent of amount]) Enthalpy Change measured using calorimeter. eg. coffee cup calorimeter. Under constant pressure, so measured heat change rH If heat released (water warms up), rH < 0 q = CmT Heat(q) is the transfer of energy between 2 systems at diff temps. U = q + w (w = -pV) U = q pV H enthalpy H = U + pV (at constant pressure) qp = H rH = sum of Hproducts sum of Hreactants H = U + RTn (when you sub in pV = nRT) Standard state of a pure substance is the most stable form at standard pressure and a specific temperature (298 K) Standard enthalpy of formation fH of a compound is the enthalpy change that results from the formation of 1 mole of the compound in a standard state from its elements under standard conditions

7. Spontaneity of reaction A reaction may be spontaneous but reaction rate may be very slow eg. H2/O2 mixture stable until there is a spark Simply lowering the energy is not the answer A hot object always cools spontaneously, never absorbs heat from colder surroundings Spontaneous reaction - one that can occur without outside intervention - thermodynamics tells us about the direction of a process not its speed - in principle a diamond should change spontaneously to graphite however VERY slow process - KINETICS tells us how fast a reaction is - THERMODYNAMICS tells us if it will proceed at all The driving force of spontaneity is an increase in the entropy of the universe Entropy a measure of the overall distribution of positions and energies in a system If we release gas molecules into a vacuum, they will spread throughout the larger volume increasing the probable particle positional and kinetic energy distribution increasing entropy

entropy a measure of disorder or probability spontaneity moving towards disorder towards state which has highest probability of existing More ways to arrange balls when mixed than separate therefore mixed state more probable similarly gas more probable than solid solid more ordered, gas more disordered Entropy: S, measures probability of the system S = R ln W W number of ways that molecules can be arranged in that configuration (often large) R gas constant Factors that affect entropy: Temperature ^ temp ^ kinetic energy ^ disposition

(a) is like a solid 2nd law of thermodynamics In any spontaneous process there is always an increase in the total entropy of the universe Suniv = Ssystem + Ssurroundings If Suniv >0 (positive) entropy of universe increases If Suniv <0 (negative) the process is spontaneous in the opposite direction If Suniv = 0 system is at equilibrium Suniv is always increasing with spontaneous processes

Not always as simple as lowering enthalpy eg. spontaneous endothermic reaction increase in disorder (number of ways of arranging products) is so great that it overcomes the tendency to go to lower energy 2nd Law Examples Heat goes spontaneously from hot to cold body Things mix spontaneously and do not un-mix (if they are miscible) soluble salt dissolves spontaneously in water, does not spontaneously crystallize (unless water is removed) Entropy is a state function, so S = Sfinal - Sinitial Suniv = Ssystem + Ssurroundings Entropy and heat To determine spontaneity (Suniv), we need to know Ssys and Ssurr How do these change during a process? The only way we can exchange energy between system and surroundings is via work or heat Need to have a thermodynamic definition of entropy containing heat flow as an important factor S can only be calculated for simple systems such as a perfect gas but is related to specific heat (number of ways a given amount of energy can be arranged in a substance Ssurr = qsurr/T = rH/T

8. Entropy change in surroundings A simple thermodynamic function related to spontaneity which only requires knowledge of system provided by the Gibbs free energy G Entropy and enthalpy Conditions for spontaneous reaction: entropy of universe increases, ie. is a maximum derivative of Suniverse = 0 for max dSuniv = 0 = dSsystem dH/T (entropy and enthalpy changes of reaction) Free energy define T dG = -(dS dH/T)=0, or dG = dH TdS = 0 Gibbs free energy: G = H-TS Because a spontaneous reaction maximizes Suniv it also minimizes G of the reaction (ie. of the system) free energy is minimized this is the driving force for chemical reactions It is a combination of enthalpy and entropy effects For a spontaneous process: G = H TS <0 if G < 0 process spontaneous G>0 reverse process is spontaneous G = 0 system is at equilibrium

G = H-TS in general neither entropy nor enthalpy dominates to influence G enthalpy energy/mole, entropy: energy/temp, put together to get free energy, energy/mole

Question At equilibrium G = 0, so find T where G = H TS = 0 a) G = 10000J + 220JK-1 x T = 0 This cannot be zero at any temperature This process has G +ve at all temps b) G = 10000J 184 J K-1 x T = 0 at T=54.3K Thus for b), below 54.3 K, G ve at 54.3, G = 0 at equilibrium G = H - T S H from measuring heat flow in calorimeter S from temp. dependence of heat capacity G is a State Function so can manipulate any number of reactions Gibbs free energy most work you can get out of a system cannot be lost to surroundings as heat therefore free to be used as work. Used to find max efficiency efficiency: max possibly (from G) / H

Strongly exothermic: energy loss dominates (entropy) Strongly endothermic: probability increase dominates A B is spontaneous if G = GB GA < 0