Module 5 - Physical chemistry and transition elements Flashcards
what is lattice enthalpy?
when gaseous ions combine to make a solid lattice, energy is given out -> lattice enthalpy
what is the standard lattice enthalpy?
- is the enthalpy change when 1 mole of ionic lattice is formed from its gaseous ions under standard conditions. its a measure of ionic bond strength. the more negative the lattice enthalpy, the stronger the bonding
what does it mean if the charge of the ions is higher?
- more energy is released when an ionic lattice forms. this is due to the stronger electrostatic forces between the ions. more energy release means that the lattice enthalpy will be more negative. so the lattice enthalpies for compounds with 2+ or 2- ions are more exothermic than those with less
what does it mean if the ionic radii of the ions involved are smaller?
- the more exothermic the lattice enthalpy. smaller ions have a higher charge density and their smaller ionic radii mean that the ions can sit closer together in the lattice. both these things mean that the attractions between the ions are stronger
how do you calculate the lattice enthalpy using a born-haber cycle?
- you start with the enthalpy of formation
- then put the enthalpies of atomisation and ionisation above this
- the electron affinity
- and lattice enthalpy goes last
what is the enthalpy of formation?
- the enthalpy change when 1 mole of a compound is formed from its elements in their standard states
what happens when a solid ionic lattice dissolves in water?
- the bonds between the ions break to give gaseous ions, this is endothermic. the enthalpy change is the opposite of the lattice enthalpy
- bonds between the gaseous ions and water are made, this is exothermic. the enthalpy change of hydration.
what is the enthalpy change of solution?
- its the overall effect on the enthalpy of these two things. the effect happens because oxygen is more electronegative than hydrogen, so it draws the bonding electrons towards itself, creating a dipole
what is the enthalpy of hydration?
- the enthalpy change when 1 mole of gaseous ions dissolves in water
what is the enthalpy of solution?
- the enthalpy change when 1 mole of solute dissolves in water
when do substances generally dissolve?
- if the energy released is roughly the same or greater than the energy taken in. so soluble substances tend to have exothermic enthalpies of solution
how do you calculate the enthalpies of hydration of ions using lattice enthalpy?
1 - put the ionic lattice and the dissolved ions at the top, connect them by the enthalpy change of solution
2 - connect the ionic lattice to the gaseous ions by the reverse of the lattice enthalpy. the breakdown of the lattice has the opposite enthalpy change to the formation of the lattice
3 - connect the gaseous ions to the dissolved ions by the hydration enthalpies of each ion
what two things affect the enthalpies of hydration?
- ions with a higher charge are better at attracting water molecules as the electrostatic attraction between the ion and the water molecules is stronger, so more energy is released when the bonds are made giving them a more exothermic enthalpy of hydration
- smaller ions have a higher charge density so they attract the water molecules better and have a more exothermic enthalpy.
what is entropy?
- its a measure of the number of ways that particles can be arranged and the number of ways that the energy can be shared out between the particles. the more disordered the particles are, the higher the entropy is. A large, positive value of entropy shows a high level of disorder.
how does physical state affect entropy?
- solid particles just unable about a fixed point - there’s hardly any randomness, so they have the lowest entropy. gas particles whizz around whenever they like. they’ve got the most random arrangements of particles, so the highest entropy
how does the number of particles affect entropy?
- the more particles you’ve got, the more ways they and their energy can be arranged and so the entropy increases
why are some reactions feasible?
substances really like disorder, they’re more energetically stable when there’s more disorder, so particles will move to increase their entropy. when reactions are feasible they just happen by themselves without addition of energy even when the enthalpy change is endothermic
what happens when a substance reaches its maximum entropy state?
its said to be thermodynamically stable. this means it wont react any further without the input of energy
what is the equation for entropy change of a reaction?
entropy change S = Sproducts - Sreactants
what is a positive entropy change?
means that a reaction is likely to be feasible, but a negative change in entropy of reaction doesnt guarantee the reaction cant happen enthalpy, temperature and kinetics play a part in whether or not a reaction occurs
what is the tendecny of a process to take place dependant on?
- the entropy, the enthalpy and the temperature. when all of these are together you get the free energy change, which tells us if a reaction is feasible,
how do you calculate the free energy change?
- free energy change = enthalpy change - temperature x entropy change
what happens when free energy change = 0?
- the reaction is just feasible, so the temperture at which the reaction becomes feasible can be calculated by
temperature = enthalpy change divided by entropy change
what happens when the enthalpy change is negative and entropy change is positive?
- the free energy change will always be negative and the reaction is feasible
what happens when the enthalpy change is positive and the entropy change is negative?
- the free energy change will always be positive and the reaction is not feasible
what happens when the free energy shows a reaction is feasible?
- it might have a high activation energy or happen very slowly
what is the reaction rate?
the change in amount of reactants or products per unit time, colorimeters measure the absorbance of a particular wavelength of light by a solution
what is the order of reaction?
the order of reaction with respect to a particular reactant tells you how the reactant’s concentration affects the rate
what is zero order?
if you double the reactant’s concentration and the rate stays the same its a zero order reaction
what is a first order?
if you double the reactant’s concentration and the rate also doubles, its a first order reaction
what is a second order?
if you double the reactant’s concentration and the rate quadruples, its a second order reaction
what is the overall order?
this is the sum of the order of all the different orders
what do the orders look like on a rate-concentration graph?
zero order - a horizontal line means changing the concentration doesn’t change the rate, so its order=0
first order - straight line through the origin means rate is proportional, so its order 1
second order - a curve means its order 2
what is the general equation for rate?
rate = k[A]m[B]n
- k is the rate constant, the bigger it is the faster it is
- m and n are the orders of the reaction with respect to reactants A and B, they tell you how the concentration of A and B affect the rate
what does it mean of the overall reaction is first order?
- then the rate constant is equal to the gradient of the rate-concentration graph of that reactant
what is the half life of the reaction?
is the time it takes for half life of the reactant to be used up.
what is the half life of a first order reaction?
its independent of the concentration so each half life will be the same length. this means the half life of a first order reaction can be read of its concentration-time graph, this is exponential decay
what is the equation to work out the rate constant using half life?
K= ln2 divided by t1/2
what happens to the rate when you increase the temperature?
more reactant particles will have the required activation energy for the reaction, so a greater proportion of the collisions will result in the reaction actually happening. so increasing the temperature, increases the reaction rate
what does a rate constant apply to?
it applies to a particular reaction at a certain temperature, so at a higher temperature the reaction will have a higher rate constant
what does Arrhenius equation?
it likes the rate constant K with Ea and temp
K = Ae x -Ea/RT
- K is rate constant, Ea is activation energy Jmol, T is temp is K, R is gas constant 8.314, and A is the pre-exponential factor
what happens as Ea gets bigger?
k gets smaller. so a large Ea, will mean a slow rate as if a reaction has a high Ea, then not many of the reactant particles will have enough energy to react. so only a few of the collisions will result in the reaction actually happening and the rate will be slow
what is Arrhenius’ equation is logarithmic form?
lnK= -Ea/RT + lnA
- you can use the eqn to create an arrhenius plot by plotting lnK against 1/T. this will make a graph of -Ea/R and y-intercept of lnA.
- You can then find Ea and A.
what are rate mechanisms?
they can have one step or series of steps. each step can have a different rate, the overall rate if decided by the step with the slowest rate which is called the RATE DETERMINING STEP
what happens if a rate appears or doesnt appear in the equation?
- if it appears in the rate reaction, it must affect the rate. so this reactant, or something derived from it must be in the rate-determining step
- if it doesnt appear in the rate reaction, then it isn’t involved in the rate determining step
what is the total pressure of a gas mixture?
- is the sum of all the partial pressures of the individual gases
what is a mole fraction?
- its the proportion of a gas mixture that is a particular gas
what is the equation for a mole fraction of a gas?
number of moles of gas divided by total number of moles of gas in the mixture
what is the equation for partial pressure of a gas?
mole fraction of a gas x total pressure of the mixture
what is the general equation for equilibrium of a partial pressure?
instead of brackets like in Kc you use p. eg p(D)d x p(E)e
what happens to the equilibrium when you change a condition of a reversible reaction?
- if the change causes more product to form, then you say the equilibrium shifts to the right
- if the change causes left product to form, then the equilibrium shifts to the left
what does the equilibrium constant for a reaction depend on?
temperature
1 - if changing the temp causes less product to form the equilibrium moves the left and the equilibrium constant decreases
2 - if changing the temp causes more product to form the equilibrium moves the right and the equilibrium constant increases
what do concentration and pressure do to the equilibrium constant (pressure)?
they dont affect the values of Kp or Kc but they do change the amounts of products and reactants present at equilibrium,
- catalysts have no effect on the position of equilibrium or the value of kc or kp.
what is the d-block?
the block of elements in the middle of the periodic table. most of the elements in the d-block are transition elements. a transition element is one that can form at least one stable ion with an incomplete d sub-shell
what can a d sub shell element do?
it can hold 10 electrons, transition elements must form at least one ion that has between 1&9 electrons in the d-subshell. all the period 4 d-block elements are transition elements except Sn and Zn.
describe chromium’s arrangement?
prefers to have one electron in each orbital of the 3d subshell and just one in the 4s subshell which gives it more stability
- when transition elements form positive ions, the s electrons are removed first, then the d electrons
describe copper’s arrangement?
prefers to have a full 3d subshell and just one electron in the 4s subshell. when cu2+ ion is formed it loses 2 electrons forming an incomplete d sub shell.
why are transition elements good catalysts?
they can change oxidation states by gaining or losing electrons within their d-orbitals. this means they can transfer electrons to speed up reactions.
- they are also good at absorbing substances onto their surfaces to lower the activation energy of reactions
what happens when you mix aq transition ions with aq NaOH or aq NH3?
you get a coloured hydroxide precipitate. in aqueous solutions, transition elements take the form (M(H20)6)n+.
describe the reactions of Copper II with NaOh and NH3?
1- [Cu(H20)6]2+ + 2OH- –> [Cu(OH)2 (H20)4]s + 2H2Ol
2- [Cu(H20)6]2+ + 2NH3 –> [Cu(OH)2 (H20)4]s + 2NH4+
solution goes from pale blue to a blue precipitate
describe the reactions of iron II with NaOH and NH3?
1- [Fe(H20)6]2+ + 2OH- –> [Fe(OH)2 (H20)4]s + 2H2Ol
2- [Fe(H20)6]2+ + 2NH3 –> [Fe(OH)2 (H20)4]s + 2NH4+
solution goes from pale green to a green precipitate, darkens on standing
describe the reactions of manganese II with NaOH and NH3?
1- [Mn(H20)6]2+ + 2OH- –> [Mn(OH)2 (H20)4]s + 2H2Ol
2- [Mn(H20)6]2+ + 2NH3 –> [Mn(OH)2 (H20)4]s + 2NH4+ solution goes from pale pink to a pink/buff solution
describe the reactions of iron III with NaOH and NH3?
1- [Fe(H20)6]3+ + 3OH- –> [Fe(OH)2 (H20)4] + 3H2O
2- [Fe(H20)6]3+ + 3NH3 –> [Fe(OH)2 (H20)4] + 3NH4+
solution goes from yellow to a orange precipitate