Application of rates and equilibrium

Application of rates:

 Small increase in temp.  large increase in rate because:

lnk = lnA – Ea/RT

 If k = small, lnA will also be small and therefore the value of –Ea/RT will be more
important – TEMP HAS A LARGE INFLUENCE ON RATE
 If k = large, rate will be high. k  1/T. Therefore if T increases by a small amount, e will
decrease a lot (k = Ae-Ea/RT) and k will increase. Increasing T, however, has little effect

Application of equilibrium:
Stotal = Ssystem + Ssurroundings
R lnK = Ssystem + (-H/T)
 Variables = T and K
 Constants = R and H
 K is only affected by a change in T because lnK  1/T. As T increases for an exothermic
reaction, -H/T becomes smaller, therefore RlnK also decreases

Haber process:
N2(g) + 3H2(g) 2NH3(g) H= -92 kJ mol-1
 Temp = 400 – 450 ̊C, Pressure = 200 atm, Catalyst = Iron
Temperature:
 RATE Increasing T = increased rate because there is an increase in KE, molecules =
increased collision energy and so more molecules reach the Ea, also as molecules move
faster, there are more collisions per unit time. Also k in the Arrhenius eqn. increases
 EQM. Exothermic reaction and so -H/T = +ve. Increasing T, reduces Stot. Therefore Kp
decreases and eqm. Shifts to the left, reducing amount product
o Temp. chosen as a balance between high rate and high yield, a catalyst is used
to increase rate (as if T = 700K). High T is also not economical due to having to
use materials that can withstand it
Pressure:
 RATE Little effect on rate
 EQM. Kp is NOT altered by increased pressure. But as its not at eqm. Increased
pressure, shifts eqm. to the RHS, increasing product yield
Catalyst:
 RATE Increases rate, providing an alternative mechanism with a lower Ea
 EQM. Does not affect position of eqm. as it does not take part in the reaction, but eqm. is
reached more quickly
Other factors:
 Never reaches eqm. because it is not a closed system
 H2 and N2 are constantly added, whilst NH3 is removed – pushes eqm. to the right,
causing even more product to be formed
 Unreacted H2 and N2 are piped round to the reactor and added again
 High pressure would favour this process but:
o Dangerous to use such a high pressured system
o Cost of making vessels strong enough to handle high pressure and of
compressing gases to such an extent

Contact Process:
 Crucial step = conversion of sulphur dioxide into sulphur trioxide (like the rate-
determining step)
2SO2(g) + O2(g) 2SO3(g) H = -196 kJ/mol
 Temp = 425 ̊C, Pressure = 2 atm, Catalyst = V2O5
Temperature:
 Increased T would increase KE and so molecules have more energy to collide more
frequently and more collision energy so there are more molecules reaching the Ea and
so there will be more successful collisions per unit time
 Reaction is exothermic so -H/T is +ve. Therefore if T increases, K will decrease
 If K decreases and Kc = [products]/[reactants], the [reactants] increase, eqm moves to
left
 However to ensure that the reaction is fast enough a higher T, of 698K, and a catalyst is
used
Pressure:
 More molecules on the LHS and so increase of pressure  greater yield, as eqm
would be pushed to the RHS
 However the yield is high enough and a high pressure = expensive (the energy
required to compress the gases, cost of ensuring that the equipment can handle the
high pressure)
At these conditions the eqm mixture contains 95% sulphur trioxide
 Not economical to increase yield further but a pressure > 1 atm is needed to drive
gases through plant
 High T increases the rate but also causes an decrease in the yield of products and so
a catalyst and a compromise T is used

Atom economy maximised by:

 Recycling unreacted gases and continuously removing products so eqm shifts to
right (also releasing SO2 into atmosphere = pollution)
 Use of heat exchangers reduces the temp. of exit gases before recycling – enables
improved conversion