A. Oxidation/Reduction 1. Working out oxidation numbers 2. Identifying what is being oxidized (reducing agent) and what is being reduced (oxidizing agent) 3. Balancing Redox reactions (using the half-equation method) B. Reaction Kinetics 4. Writing Reaction Rate Laws & Calculating the specific constant k C. Acid/Base solutions 5. Calculating the pH of a solution of a. strong acid/base & b. weak acid/base 6. Interpreting Titration Curves
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The oxidation state of an uncombined element is zero. That's obviously so, because it hasn't been either oxidized or reduced yet! This applies whatever the structure of the element - whether it is, for example, Xe or Cl2 or S8, or whether it has a giant structure like carbon or silicon. The sum of the oxidation states of all the atoms or ions in a neutral compound is zero. The sum of the oxidation states of all the atoms in an ion is equal to the charge on the ion. The more electronegative element in a substance is given a negative oxidation state. The less electronegative one is given a positive oxidation state. Remember that fluorine is the most electronegative element with oxygen second. Some elements almost always have the same oxidation states in their compounds:
usual oxidation state always +1 always +2 except in peroxides and F2O (see below) except in metal hydrides where it is -1 (see below)
element
exceptions
Oxygen
usually -2
Hydrogen
usually +1
Fluorine
always -1
Chlorine
usually -1
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Examples of working out oxidation states What is the oxidation state of chromium in Cr2+? That's easy! For a simple ion like this, the oxidation state is the charge on the ion - in other words: +2 (Don't forget the + sign.) What is the oxidation state of chromium in CrCl3? This is a neutral compound so the sum of the oxidation states is zero. Chlorine has an oxidation state of -1. If the oxidation state of chromium is n: n + 3(-1) = 0 n = +3 (Again, don't forget the + sign!) What is the oxidation state of chromium in the dichromate ion, Cr2O72-? The oxidation state of the oxygen is -2, and the sum of the oxidation states is equal to the charge on the ion. Don't forget that there are 2 chromium atoms present. 2n + 7(-2) = -2 n = +6
Warning: Because these are simple sums it is tempting to try to do them in your head. If it matters (like in an exam) write them down using as many steps as you need so that there is no chance of making careless mistakes. Your examiners aren't going to be impressed by your mental arithmetic - all they want is the right answer!
2. Using oxidation states to identify what's been oxidized and what's been reduced
In each of the following examples, we have to decide whether the reaction involves redox, and if so what has been oxidized and what reduced. Example 1: 0 +1/ -1 +2/-1 0
Mg + 2HCl MgCl2 + H2 Have the oxidation states of anything changed? Yes they have - you have two elements which are in compounds on one side of the equation and as uncombined elements on the other. Check all the oxidation states to be sure: The magnesium's oxidation state has increased - it has been oxidised. The hydrogen's oxidation state has fallen - it has been reduced. The chlorine is in the same oxidation state on both sides of the equation - it hasn't been oxidised or reduced.
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NaOH + HCl NaCl + H2O Checking all the oxidation states: Nothing has changed. This is not a redox reaction.
I- I2 MnO4- Mn2+
3) To balance the atoms of each half-reaction, first balance all of the atoms except H and O. For an acidic solution, next add H2O to balance the O atoms and H+ to balance the H atoms. Balance the iodine atoms: 2 I- I2 The Mn in the permanganate reaction is already balanced, so let's balance the oxygen: MnO4- Mn2+ + 4 H2O Add H+ to balance the 4 waters molecules: (4 x 2 H is needed) MnO4- + 8 H+ Mn2+ + 4 H2O
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4) Adding electrons to the reactions (e- added where ox.number is decreased) 2 I- I2 + 2e(each of the two I- ions loses an electron: Oxidation is loss of e-: OIL)
5 e- + 8 H+ + MnO4- Mn2+ + 4 H2O (Mn with ox.no. +7 gains 5 e- to be reduced to Mn+2 Reduction is gain of e-: RIG) 5) Now multiply the two half-reactions by numbers that will make them both have the same number of electrons (in this case 10e- is the lowest whole number common to 2 and 5) 5(2I- I2 +2e-) 2(5e- + 8H+ + MnO4- Mn2+ + 4H2O) 5) Now add the two half-reactions: Get the overall equation by canceling out the electrons, H2O, and H+ that may appear on both sides of the equation (here only electrons canceled out) 10 I 5 I2 + 10 e-
16 H+ + 2 MnO4- + 10 e- 2 Mn2+ + 8 H2O This yields the following final equation: 10 I- + 16 H+ + 2 MnO4- 5 I2 + 2 Mn2+ + 8 H2O
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B. Reaction Kinetics
(a) Deduce the order of reaction with respect to reactant A. Compare expts. 2 and 3. [B] is kept constant, but on halving A the rate is reduced by a factor of 1/4 (1/2 x 1 /2) so the rate is proportional to [A]2. Therefore the order with respect to A is 2 or 2nd order. You can think the other way round i.e. from expt. 3 to 2, [A] is doubled and the rate quadruples. (b) Deduce the order of reaction with respect to reactant B. Compare expts. 1 and 2. [A] is kept constant but doubling [B] doubles the rate, so the reaction is directly proportional to [B]. Therefore the order with respect to B is 1 or 1st order. Similarly comparing expts. 1 and 4 (4x [B] gives 4x rate). (c) the overall order of the reaction between A and B: Total order = 2 + 1 = 3, 3rd order overall. (d) Write out the full rate expression. rate = k [A]2 [B] (e) Calculate the value and units of the rate constant. rearranging rate = k [A]2 [B] gives k = rate / [A]2 [B] and the units will be mol L-1s-1 / (mol L-1)2(mol L-1) = s-1 / (mol L-1)2 = mol-2 L2 s-1 so, using the data from expt. 1 (or any set, assuming data perfect) gives
C. Acid/Base solutions
pH
[ H3O+ ]
pH + pOH = 14
[ H3O+ ] [ OH ] = 1 x 1014
pOH
[ OH ]
pH = log [ H3O+ ]
( or pH = log [ H+ ] )
1)
Determine the pH of the following solutions: a) b) A 4.5 x 10-3 M HBr solution. A 3.67 x 10-5 M KOH solution. pH = 2.4 pH = 9.56
2)
What are the pOHs for the solutions in problem 1? a) 11.6 b) 4.44 c) 12.9 d) 11.8
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STEP 2 Make the following assumptions: 1. [H+]equilibrium = [A-]equilibrium = x 2. [HA]equilibrium = [HA]initial Weak acids are rarely ionized to a large degree. STEP 3 Use the Ka expression, and solve for x.
EXAMPLE Vinegar is a dilute water solution of acetic acid with small amounts of other components. Calculate the pH of bottled vinegar that is 0.667 M HC2H3O2, assuming that none of the other components affect the acidity of the solution. (Ka= 1.8 x10-5) HA H+(aq) + A-(aq)
Ka= 1.8 x10-5 = x2 = 1.2 10-5 [H+] = 3.5 10-3 M = 3.5 10-3 pH = -log(3.5 10-3) = 2.46
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6. Titration Curves:
A graph of sample pH versus volume of titrant is called a titration curve. Titrations involving different combinations of acid and base species produce a variety of characteristic titration curves. (The following generalizations apply to acid and base species that have molar concentrations of 0.100 M.)
There are fewer useful indicators for titrations involving weak species than there are for strong acid-strong base titrations. The equivalence point for strong acid-strong base titrations occurs at pH 7. The equivalence point for a weak base-strong acid titration is less than pH 7. The equivalence point for a strong base-weak acid titration is greater than pH 7.
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