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2 10113151TutSetS117 PDF
2 10113151TutSetS117 PDF
CONTENTS
It is assumed that you will have attempted all of the problems in each tutorial set before the end-of-semester
examination. The examinable material is as detailed in the syllabus, the exercises in the tutorial sets, and in the
laboratory assignments.
IMPORTANT NOTE: No written answers will be provided for these questions. You are expected to attempt the
relevant questions BEFORE tutorial class, and use the time in class to ask questions and record the correct written
method for any questions with which you are having difficulty. For this reason, attendance at tutorials is compulsory.
PAGE 2
1 2
H
The Periodic Table He
1.008 4.003
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.99 24.31 26.98 28.09 30.97 32.07 35.45 39.95
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.93 58.69 63.55 65.39 69.72 72.59 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo 99Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 (98.91) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi 210Po 210At 222Rn
132.9 137.3 138.9 178.5 180.9 183.9 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 (210.0) (210.0) (222.0)
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd 145Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
KEY 140.1 140.9 144.2 (144.9) 150.0 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0
For radioactive elements the relative atomic mass of the most common isotope is given in parentheses, and the mass number for that isotope is given as a superscript
1. Two conventions are in common use for the graphical and tabular representation of data:
(a) The physical quantity is followed by the unit in parentheses:
e.g. mass (g), pressure (Pa), H (kJ mol1), k (105 L mol 1 s1)
(b) The better method is to divide the physical quantity by the unit, thus giving a number:
e.g. mass/g, pressure/Pa, H/kJ mol1, k/105 L mol 1 s1 or 105 k/ L mol 1 s1
Both conventions are used in chemistry.
2. Although the SI unit of volume is m3, the units more often used in chemistry are dm3 (or litre, L) and cm3 (or
mL). In these tutorial notes a variety of units has purposely been used.
3. The SI unit of pressure is the pascal (1 Pa = 1 N m2). However, 1 Pa is a very small pressure and multiples
such as kPa (i.e. 103 Pa), MPa (i.e. 106 Pa) are often used. Other units in common use are:
- the bar (1 bar = 105 Pa). A pressure of 1 bar is the standard state pressure for thermochemical data, and is
used in some books, e.g. SI Chemical Data;
- the standard atmosphere (atm, 1 atm = 1.013 105 Pa). A pressure of 1 atm is the pressure used in defining
the normal boiling temperature of a liquid and normal melting point of a solid.
- the mmHg or Torr. These are defined differently but are practically identical (both equal 133.3 Pa or
1 atm/760).
similar convention should be used for a balanced chemical equation. mol 1 means per mole of reactants or
products in the stoichiometric mixture as given by the specified equation, eg:
(This indicates that H = 564 kJ per mole of O2(g) consumed or per 2 moles of CO(g) consumed or per two
moles of CO2 produced.)
Note: When naming an isolated cation or anion then the name of the ion must be followed by the word ion,
e.g. Cl would be written or said as "chloride ion" or "chloride anion".
In science, if you record too few significant figures, you risk creating an error because you have dropped digits which
were part of the original measurement. If you record too many significant figures, you are overstating the accuracy of
your measurements. Hence, when you compare your results to values in the scientific literature, differences may seem
significant when they are not.
This section is designed as a quick guide to assist you in your studies. Please read the entire section carefully.
Improper use of significant figures in assignments, lab reports, or exams may result in deducted marks.
--------------------------------------------------------------------------------------------------- --------------------------------------------
Identification
Here are some example numbers and how they are classified in terms of their decimal places and significant figures.
Note that zeroes which only show the size of a value are not considered significant.
Number Decimal Places Significant Figures Number Decimal Places Significant Figures
1200 0 2 (maybe*) 0.120 3 3
1200.0 1 5 0.012 3 2**
12.0 1 3 0.0012 4 2**
0.12 2 2 1.0012 4 5
* Zeroes which occur just before a decimal point (such as in the example above) are ambiguous: they may or may not be significant.
** Zeroes which occur just after a decimal point and are not preceded by any significant figures (such as in the examples above), are
also NOT considered significant.
Calculations
When performing a calculation, consider the following steps:
Check the number of significant figures and decimal places in each value you are given (either in the question
or in the data available).
When adding or subtracting values, your answer must have the same number of decimal places as the value
above with the fewest decimal places.
When multiplying or dividing values, your answer must have the same number of significant figures as the
value above with the fewest significant figures.
When applying a logarithm, the number of decimal places in the answer needs to match the number of
significant figures in the value we applied (see the example below for more detail).
Do not round any of intermediate values until the very end of your calculation.
o If you are using the resulting number in a further calculation, use the un-rounded value in your next
calculation.
NOTE: Some numbers in a calculation are exact numbers (eg: 2 sodium atoms in Na2CO3, 1000 g in a kg, an n=3
energy level, etc). Whilst an exact number of 2 can be written in the form 2, this actually means 2.0000000000
with an infinite number of significant figures. Therefore, exact numbers should NOT affect the number of significant
figures in your calculation.
Example Questions
Here are a few examples, increasing in level of difficulty:
Question 1 Adding/Subtracting Values
2.347 g of solid calcium carbonate is added to a beaker containing 20.0 g of calcium carbonate. How much
calcium carbonate is now in the beaker?
Working
2.347 g + 20.0 g = 22.347 g (based on the calculator display).
Now lets look at the decimal places (since were adding values):
2.347 g has 3 decimal places
20.0 g has 1 decimal place
Therefore our answer needs to be expressed to 1 decimal place
22.347 expressed to 1 decimal place is 22.3.
Answer
Hence our final answer to this question should be written as 22.3 g.
The justification behind why logarithms behave like this is slightly complicated. However, if you are really interested in
finding out the answer to this mathematical subtlety, please ask your tutors or approach the Duty Tutor in the Chemistry
Student Study Area (see Moodle for details).
For more information, you can also see the following resources:
Uncertainties and Significant Figures: Blackman (et al.) Chemistry, 2nd edition.
Wiley & Sons. (Page 30-32)
Significant Figures in Calculations: Morris Hein, Susan Arena (2012) Foundations of College Chemistry,
14th edition. Wiley & Sons. (Page 18-21)
Rounding and Significant Figures: http://www.purplemath.com/modules/rounding2.htm
Significant Figure Rules: http://chemistry.bd.psu.edu/jircitano/sigfigs.html
Rules (and tips for logarithms/antilogarithms): http://www.ndt-
ed.org/GeneralResources/SigFigs/SigFigs.htm
Sig Figs and Logs: http://www2.chemistry.msu.edu/courses/cem262/sigfigsandlogs.pdf
Although certain rules are adopted in the naming of compounds (i.e. nomenclature) there is not just one universally
accepted system used to name all compounds. The most common system of nomenclature is that laid down by
I.U.P.A.C (International Union of Pure and Applied Chemistry). Even this system has found it necessary to recognize
certain exceptions. Remnants of some of the older systems still remain in the chemical language.
Some of the simple rules for naming compounds are illustrated in the following selfinstruction ('do it yourself' or
'DIY') tutorial. This tutorial assumes a familiarity with the names and symbols of the elements and their periodic
classification. Each section of the tutorial begins with an informative statement, S, and the frames which follow it
contain questions relevant to that statement. In using the tutorial, you should cover the answers, attempt to answer
the questions and then immediately check your answer by uncovering the next line. If your answer is wrong you
should not proceed with the tutorial until you know why your answer is wrong, what remedial action you should take in
order to get the correct answer, and what you should do so as not to make the same error in the future.
S1 Some of the elements have names which are derived from the Latin; others have been Anglicized, but the
symbol for them is derived from the Latin; others have Greek or other origins. Most of the new synthetic elements are
named after famous scientists or scientific establishments. Some of the elements whose names are of Latin origin
(which remains only in their symbol) are given below:
A positively charged ion is called a cation; a negatively charged ion is called an anion. Metals, especially those
elements on the left hand side of the Periodic Table form cations; those in Group 1 (Li Cs), lose 1 electron, show a
charge of +1 (oxidation state) and those in Group 2 (Be Ba) of +2. Nonmetals on the right hand side in Group 17
(F I), gain 1 electron, form anions of 1 charge and those in Group 16 (O Te) of 2. The nonmetals in groups 13
15, i.e. B, C and N groups and the transition metals, as well as a few others, show several oxidation states.
When two different elements combine, a binary compound is formed. Such compounds are named by stating first the
name of the cation (or less negative of the two atoms) and then the name of the anion (or more negative atom). The
names of the anions end in ide if the anions are formed from the elements. A vowel preceding the last syllable is
dropped, i.e. oxygen becomes oxide (not oxyide). Some elemental names drop more than one syllable, e.g. nitrogen
and phosphorus become nitride and phosphide (not nitrogide and phosphoride).
A summary of the common oxidation states of the elements in the main groups in the Periodic Table is given below.
For the purposes of nomenclature it is necessary to decide which of two elements is the more negative. For
nomenclature purposes ONLY, the following order of negativity is used:
B, C, P, H, N, Se, I, Br, Cl, O, F.
A.5 (a) sodium bromide Q.6 What would be the formula for
(b) potassium sulfide binary compounds formed from:
(c) magnesium oxide (a) calcium and phosphorus
(d) barium chloride (b) strontium and fluorine
(e) lithium nitride (c) silicon and carbon
(f) silver iodide (d) hydrogen and sulfur
(e) potassium and hydrogen
(f) boron and nitrogen
A.6 (a) calcium phosphide Ca 3P2
(b) strontium fluoride SrF2
(c) silicon carbide SiC
(d) hydrogen sulfide H2S
(e) potassium hydride KH
(f) boron nitride BN
S3 A few common binary compounds containing hydrogen are known by their common or trivial names. These are
given in Q.7.
When more than one binary compound is possible between two nonmetal elements, the prefixes mono, di, tri, tetra,
penta and hexa are used to indicate 1, 2, 3, 4, 5 or 6 atoms.
S4 Polyatomic ions are groups of atoms which have acquired a positive or negative charge and behave as if they
+
were a single unit. The most common polyatomic cation is the ammonium ion, NH 4 . The names of some common
anions are:
OH hydroxide NH2 amide
2
O2 peroxide CN cyanide
S-5 Some elements can combine with other elements to form more than one compound (i.e. show more than one
oxidation state). The compound formed depends upon the conditions used for its preparation. In order to distinguish
between these compounds, their names have to indicate the ratio in which the elements have combined. One of the
ways in which this is done is to use the prefix di, tri, etc. The prefix mono is frequently omitted. This system is
especially suitable for binary compounds of nonmetals and is sometimes used for those of metals as well. This system
is being superseded although it is still retained completely in the names of some very common compounds such as
sulfur dioxide and sulfur trioxide.
S7 Oxygen forms polyatomic anions with all other nonmetals, except fluorine, and with some metals, e.g.
manganese, chromium, etc. Oxyanions can be formed between oxygen and the second row elements boron, carbon and
nitrogen. These atoms are small atoms and the maximum number of oxygen atoms able to be located around any one of
3 2 2
these is three. Oxyanions BO2 , BO3 , CO3 , NO2 and NO3 are formed. (Notice there is no CO 2 or CO2 ).
Oxyanions between oxygen and the elements in the third and higher rows have a maximum of four oxygen atoms
3- 3 2 2
arranged around the central atom, e.g. PO3 , PO4 , SO3 , SO4 . When the maximum number of oxygen atoms
surrounds an element in groups 13, 14, 15 or 16, the oxyanion has the ending ate added usually to the stem of the
name of the element. When one oxygen less is bonded to the central atom, the ending is ite (except for BO2 which is
a metaborate). The system of naming compounds containing these polyatomic anions is similar to that used for naming
binary compounds. The formulae and names of the common oxyanions and the anion of the elements in Groups 14, 15
and 16 are given below.
2 2
Group 16 SO4 sulfate SO3 sulfite S2 sulfide (Note: All are 2 anions)
Group 15 NO3 nitrate NO2 nitrite N3 nitride
(Note: Nitride is 3 BUT nitrate and nitrite are 1)
3 3
PO4 phosphate PO3 phosphite P3 phosphide
(Note: All are 3)
3 3
AsO4 arsenate AsO3 orthoarsenite
2 2
Group 14 CO3 carbonate SiO3 silicate
A.17 (a) phosphite ion Q.18 What would be the formula for
(b) sulfite ion (a) nitride ion (b) phosphate ion
(c) carbonate ion (c) sulfate ion (d) arsenate ion
(d) nitrate ion
(e) borate ion
(f) nitrite ion
3
A.18 (a) N3 (b) PO4 Q.19 Name the following:
2 3 (a) CaSO3 (b) MnSO4 (c) FePO4
(c) SO4 (d) AsO4
(d) Ag2CO3
A.19 (a) calcium sulfite Q.20 What would be the formula for:
(b) manganese(II) sulfate (a) potassium sulfate
(c) iron(III) phosphate (b) aluminium phosphate
(d) silver carbonate (c) strontium sulfite
(d) lead nitrite
(e) ammonium carbonate
A.20 (a) K2SO4 (b) AlPO4
(c) SrSO3 (d) Pb(NO2)2
(e) (NH4)2CO3
S8 Oxyanions containing the halogens (except fluorine) follow a slightly different pattern of nomenclature to that in
S7 in order to allow oxyanions containing 1, 2, 3 or 4 oxygen atoms to be named systematically. The ending ate
added to the stem name is given to the anion containing 3 oxygen atoms and ite to that containing 2. The prefix per
(a contraction of hyper, meaning over or higher) is given to that containing 4 oxygen atoms and the prefix hypo
(meaning under or lower) to that containing one oxygen atom. Notice that all of them, like the simple anion, X , have a
charge of 1.
hypo ite XO where X = Cl, Br or I
ite XO2 e.g. ClO is hypochlorite ion
ate XO3 BrO2 is bromite ion
per ate XO4 IO3 is iodate ion
ClO4 is perchlorate ion
A.21 (a) hypoiodite ion Q.22 What would be the formula for:
(b) bromate ion (a) sodium hypobromite
(c) chlorite ion (b) magnesium perchlorate
(d) periodate ion (c) potassium iodate
(d) calcium hypochlorite
A.22 (a) NaOBr or NaBrO
(b) Mg(ClO4)2 (c) KIO3
(d) Ca(ClO)2
S9 If the neutral hydrogen compound of these oxyanions dissolves in water to form an acidic solution, the ite
ending of the anion is changed to ous and the ate ending becomes ic, and the word acid is added.
A.23 (a) hypochlorous acid Q.24 What would be the formula for:
(b) periodic acid (a) nitrous acid (b) phosphoric acid
(c) bromous acid (c) silicic acid (d) boric acid
(e) hydrofluoric acid
(f) chloric acid
A.24 (a) HNO2 (b) H3PO4
(c) H2SiO3 (d) H3BO3
(e) HF (f) HClO3
S10 As stated in S7, oxygen forms anions with some metals. The commonest of these oxyanions are the
permanganate ion, chromate ion, and dichromate ion. In all oxyanions, the oxidation state of oxygen is 2. The
oxidation state of manganese in MnO4 is therefore +7 in order for MnO 4 to be 1 (i.e. Mn (+7), 4(O) = 4 x 2 = 8,
overall +7 8 = 1). In ClO4 the oxidation state of chlorine is +7 and the anion is called perchlorate; in MnO 4 the
oxidation state of the central atom is +7 and the anion is called permanganate. Similarly, the oxidation state of sulfur
2 2
in SO4 is +6; this is the same as the oxidation state of chromium in the chromate ion, CrO 4 .
S11 Another important kind of polyatomic anion is formed from polyprotic acids. These type of anions are formed
when one or two protons (but not all the available protons) are reacted with bases. The resulting anions then contain
hydrogen and may also contain oxygen: this is reflected in the name and formula
2
e.g. H+ + CO3 HCO3 (hydrogencarbonate anion)
2
A.26 (a) HSO3 (b) HPO4 Q.27 Name the following
(a) Na2HPO4 (b) NaH2PO4
(c) H2PO4 (d) HS
(c) NH4HSO4
S12 Water of crystallisation may be indicated by (Greek prefix) hydrate or by numbers to indicate the relative
numbers of each formula: e.g. Na2SO4.10 H2O is sodium sulfate decahydrate or sodium sulfate tenwater.
ammonia NH3
In any study of chemistry it is essential that you can write chemical names and formulae correctly and almost
automatically. This is an important first step in being able to use one aspect of the vocabulary of chemistry. Without
this proficiency, you are chemically illiterate and your difficulties in trying to master other topics in chemistry will be
compounded.
References: Blackman, et al. 'Chemistry': 1.2 1.4, 3.1 3.6, 6.1 6.6
CHEM1011 and CHEM1031/1051 may proceed at different rates through this problem set.
NOTE: You are expected to know the names and symbols of at least the first 36 elements and the symbols for other
common elements such as tin, lead, gold, silver, and mercury. You should have completed the 'Naming of Chemical
Compounds' selfinstruction tutorial earlier in this course pack.
Pressure units: 1 atm = 760 mmHg = 760 Torr = 1.013 105 Pa.
(ii) 80 46 36
81
(iii) Br
(iv) 25 55 23
(b) Protium, deuterium and tritium are isotopes of hydrogen. Write the symbols which identify atoms of
these isotopes and comment on any expected differences in their physical and chemical properties.
(c) Calculate the average atomic mass of sulfur from this data for its four naturally occurring isotopes:
isotopic mass number percent abundance isotopic mass
32 95.0 31.97207
33 0.760 32.97146
34 4.22 33.96786
36 0.0140 35.96709
3. (a) Write the chemical formula for each of the following:
(i) sodium chloride (ii) magnesium bromide (v) copper(I) chloride
(ii) carbon dioxide (iv) magnesium oxide (vi) copper(II) chloride
4. Write the unambiguous chemical name for each of the following acids in aqueous solution.
(a) HClO (d) HClO4 (g) HNO2 (j) HF
5. Balance the following equations the final equation should show the lowest whole number coefficients of
reactants and products.
(a) C4H9OH + O2 CO2 + H2O
6. (a) Determine the number of oxygen atoms contained in 1.10 mol of aluminium chlorate hexahydrate.
(b) Determine the amount (mol) of chromium atoms in 140.0 g chromium(III) oxide.
(d) Calculate the mass of copper(I) sulfide which contains 4.6 1023 copper atoms.
(e) How many grams of ethanol (C2H5OH) must be added to 90.0 g water to make a solution containing
equal numbers of ethanol and water molecules?
9. (a) Calculate the molarity of the cation in each of the following solutions.
(i) 2.30 M MgCl2 (ii) 2.30 M MgSO4 (v) 1.50 M Na3PO4
(iii) 1.50 M NaCl (iv) 1.50 M Na2SO4
10. (a) Calculate the volume of concentrated reagent required to make the following dilute solutions:
(i) 18.0 M H2SO4, to make 5.0 L of 5.0 M H2SO4.
3
(ii) 15 M NH3, to make 500 cm of 1.2 M NH3.
(b) Calculate the mass of solute required to make:
3
(i) 250 cm of 0.050 M sodium carbonate
3
(ii) 10.0 cm of 0.100 M Fe(NH4)2(SO4)2.6H2O
(c) How many litres of 0.200 M NaOH solution may be prepared from 50.0 g of NaOH pellets?
(d) What is the minimum volume of 0.1060 M AgNO3 must be reacted with 125 mL of 0.0862 M K2CrO4 to
precipitate all the chromate ions as Ag2CrO4?
(e) It is desired to prepare 250.0 mL of a standard solution having a concentration of 0.1000 M AgNO 3.
How many grams of a sample of AgNO3 of 98.8 % purity are required for this purpose?
(f) A 20.0 mL sample of 0.15 M calcium chloride (CaCl 2) solution was pipetted into a 100.0 mL volumetric
flask, which was made up to the 100.0 mL mark by adding water. What is the concentration of chloride
ions in the final, mixed, solution?
(g) It is desired to make 250.0 mL of 0.010 M sulfuric acid solution, by diluting the 0.100 M solution
provided in the lab. What volume of 0.100 M sulfuric acid needs to be measured out and diluted to the
250.0 mL final volume?
1 1
11. Saccharin (molar mass = 183.18 g mol ) and calcium cyclamate (molar mass = 396.55 g mol ) are substitutes
for sugar.
(a) Calculate the percentage, by mass, of each element in Ca(C 6H11NHSO3)2 (calcium cyclamate)
(b) The composition of saccharin is 45.89 % carbon, 2.75 % hydrogen, 26.20 % oxygen, 7.65 % nitrogen and
17.51 % sulfur by mass. Determine the empirical formula and the molecular formula of saccharin.
12. Write balanced ionic equations for the following chemical reactions. Include the state of matter of each species
but do not include spectator ions.
Example: Solid calcium sulfite reacts with hydrochloric acid to give sulfur dioxide gas.
Overall equation: CaSO (s) + 2 HCl(aq) SO (g) + H O(l) + CaCl2(aq)
3 2 2
+ 2+
Net ionic equation: CaSO3(s) + 2 H (aq) SO2(g) + H2O(l) + Ca (aq)
(a) Solid strontium carbonate reacts with hydrochloric acid to give gaseous carbon dioxide.
(b) Lead nitrate solution, when mixed with sodium iodide solution, gives a yellow precipitate of lead iodide.
13. Teaspoons made from a certain alloy containing the elements bismuth, lead, tin and indium are not
recommended for stirring sugar into hot coffee, as the alloy melts at 58 C. A sample of the alloy, weighing
5.038 g, was treated in such a way as to convert the tin to 0.742 g SnO2, the lead to 1.298 g PbSO4 and the
bismuth to 2.780 g Bi2O3. What is the percentage, by mass, of each of the four elements in the alloy sample?
14. (a) A sample of concentrated hydrochloric acid was prepared by passing HCl gas into distilled water. The
3
resultant acid solution had a density of 1.18 g cm at 25C. Analysis showed that 20.0 g of the
concentrated acid contained 8.16 g of HCl.
(i) How many grams of HCl are contained in 100.0 g of the concentrated acid?
(ii) What is the percent by mass, of water in the concentrated acid?
(iii) Calculate the mass of HCl contained in 1.00 L of the concentrated acid.
(iv) How many moles of HCl are contained in 1.00 L of the acid solution?
(b) An aqueous solution containing 100.0 g of ethanol, CH3CH2OH, per litre of solution has a density of
3
0.984 g cm . Calculate:
(i) the molarity of CH3CH2OH
(ii) the molality of CH3CH2OH in this solution, and
(iii) the mole fraction of CH3CH2OH in this solution.
15. One of the methods of separating Uranium-235 (a nuclear fuel) from uranium-238 (non fuel) is by the effusion
235 238 235 238
of their gaseous hexafluorides, ( UF6 and UF6). How much faster will UF6 effuse than UF6? Use
235 238
the following atomic masses (in amu): U: 235.119, U: 238.125, F: 18.99840
16. A 3.92 g sample of a pure ammonium salt NH4X (X is an unknown monatomic anion) was analysed by
treatment with excess NaOH, liberating NH3(g) which was absorbed in 250.0 mL of a 0.400 M solution of
H2SO4. The excess H2SO4 was titrated with 2.00 M NaOH and required 80.0 mL for neutralization.
17. (a) The volume of a gas is 45.0 L at 45 C and 750 mmHg. What volume will it occupy at 25 C and 1 atm
pressure?
(b) Calculate the density of gaseous CH4 at 50 C and 1.20 atm.
(c) Calculate the molar mass of a gas if 0.455 g occupies a volume of 250 mL at 27 C and 772 mmHg.
(d) The number of CH4 molecules in a gas mixture is four times the number of C2H4 molecules. The partial
pressure of CH4 is 100 mmHg. What is the partial pressure of C2H4 in the mixture?
19. (a) Ethane gas, C2H6, burns in air as indicated by the equation:
2 C2H6(g) + 7 O2(g) 4 CO2(g) + 6 H2O(g)
20. (a) A sample (0.499 g) of a gaseous compound Q containing only carbon and hydrogen was burned. Carbon
dioxide (1.566 g) was recovered. Determine the empirical formula for Q.
1
(b) The density of Q at 50 C and 0.948 atm was 1.50 g L . Determine the molecular formula of Q.
(c) What volume of 0.245 M NaOH would be required to react with the carbon dioxide produced in (a)?
NUMERICAL ANSWERS
2. (c) 32.1
24 2
6. (a) 9.93 x 10 ; (b) 1.842; (c) 360 g; (d) 61 g; (e) 2.30 x 10 g
7. 41.5 g
9. (a) (i) 2.30 M (ii) 2.30 M (iii) 1.50 M (iv) 3.00 M (v) 4.50 M
10. (a) (i) 1.4 L; (ii) 0.040 L (b) (i) 1.3 g; (ii) 0.392 g (c) 6.25 L (d) 203 mL; (e) 4.30 g; (f) 0.06 M;
(g) 25.0 mL.
11. (a) 10.11 % Ca, 36.34 % C, 6.10 % H, 7.07 % N, 16.17 % S, 24.21 % O; (b) C7H5O3NS
13. 11.60 % Sn, 17.60 % Pb, 49.50 % Bi, 21.30 % In
14. (a) (i) 40.8 g (ii) 59.2 % H2O; (iii) 481 g; (iv) 13.2 mol
(b) (i) 2.171 M; (ii) 2.46 molal; (iii) Xethanol = 0.042;
15. 1.0043 times faster
16. Br
1 1
17. (a) 41.6 L (b) 0.73 g L (c) 44.1 g mol (d) 25 mm Hg
4 3 22
18. (a) PO = 2.1 x 10 Pa; (b) O2 conc. = 9.4 mol m ; (c) 29; (d) 6.5 x 10 ;
2
19. (a) (i) 87.5 L; (ii) 417 L; (iii) 50.0 L; (b) (i) 450 Torr; (ii) 500 Torr;
20. (a) CH2; (b) C3H6; (c) 290 mL.
2. The wavelengths of light emitted by atomic hydrogen are given by the equation:
1 1 1
RH
n12 n22
7 1
where RH is the Rydberg constant for hydrogen with the value RH = 1.096776 10 m .
(a) The Lyman series in the spectrum of the hydrogen atom originate from transitions for which the lower
energy level has n = 1. Calculate the wavenumber (either in m1 or cm1), wavelength (either in nm or m)
and the frequency (s1 or Hz) of the two longest wavelength lines in the Lyman series (speed of light is
8 1
c = 2.99792458 10 ms ). Indicate the region of the spectrum corresponding to these transitions.
(b) If the electron of the hydrogen atom is raised from the lowest energy level (n = 1) to the energy level
n = , the electron becomes free of the atom and the H +(g) ion is produced. Calculate the energy required
for this process (in J atom1 and in kJ mol1).
ml
ms
(b) What is the maximum number of electrons that can be accommodated in:
(i) all orbitals with n = 6, l = 1?
(ii) all sublevels with n = 4?
7. (a) Using the Aufbau principle and arrows-in-labelled-boxes notation, write the ground state electronic
configurations for the following isolated atoms or ions:
(i) N; Be; K; C
(ii) Cu; Fe; Ti; Ni
2+ + 2+ 3+
(iii) Ti ; Na ; Fe ; Cr
3 2
(iv) F ; H ; N ; Se
(b) Write the ground state configurations of each of the above species using 1s1 notation.
(c) Write the formulae for two cations and two anions which are isoelectronic with argon. Which of these
ions has the largest ionic radius?
(d) Which of the ions in (a) (iii) are paramagnetic?
CHEM1031/1051 only
8. This question will require you to do some research using whatever resources you choose.
(a) What is a Rydberg atom?
(b) What are typical quantum numbers for an electron in a Rydberg atom?
(c) How large is a regular atom compared to the wavelength of visible light? How large is a Rydberg atom?
(d) Why are Rydberg atoms very fragile?
NUMERICAL ANSWERS
1. (d) 2.96 1019 J.
2. (a) 8.225820 106 m1; 121.5684 nm; 2.466039 1015 Hz and 9.749120 106 m1; 102.5734 nm;
2.922713 1015 Hz. (b) 2.178686 1018 J atom1; 1312 kJ mol1.
3. (c) 15.
4. (b) (i) 6 (ii) 32.
1. (a) Explain what is meant by: (i) atomic radius (ii) ionic radius.
(b) Is a cation smaller or larger than its parent atom?
(c) Circle the species in each part that best fits the description given:
(i) the largest atomic radius:
K, Na, Mg, Al, S, Cl, Br
(ii) the largest ionic radius:
2- 3 + 2+ 3+
O , F , N , Na , Mg , Al
(iii) a isolated paramagnetic ion:
+ 2+ + 2+ 3+
K , Ni , Cu , Zn , Sc
(iv) the smaller ionic radius:
2+ 3+
Fe , Fe
(v) the most electronegative element:
Na, Cs, P, Al, Cl, I
2. For each part below make a rough sketch of the shape of the periodic table and shade in the region described.
(a) elements with the lowest first ionization energy
(b) elements with the most exothermic electron affinity
(c) elements with the highest electronegativity
(d) elements which have the largest atomic radius in their group
(e) elements which have the largest atomic radius in their period
3. In each of the following pairs, which would be the larger ion? Give a reason for your answer.
2 2 2 + 3+
(a) O and F (b) S and Se (c) Tl and Tl
+ 2+ + + + 3+
(d) Cu and Zn (e) Na and K (f) K and Sc
CHEM1031/1051 only
6. (a) Define the terms: (i) first ionization enthalpy and
(ii) second ionization enthalpy
(b) (i) Without using actual values, summarize the trend of first ionization enthalpy (I.E.) for the elements
with atomic numbers 10 to 18 by plotting 1st I.E. versus atomic number
State briefly the general periodic changes in first ionization enthalpy, and any irregularities which
occur. Suggest reasons.
(ii) On the same axes plot the variation of second ionization enthalpy for the same elements. Give
reason(s) for the features in the plot and compare with (i).
7. Which element am I?
(a) I have a high electron affinity. The element on my left in the Periodic Table has a lower electron affinity.
The element on my right in the Periodic Table has a higher ionization energy and basically no electron
affinity. I am toxic in my elemental state, but I am very commonly found in my non-toxic ionic state.
Within my group, I have the second highest ionization energy.
(b) I am a metal. My atomic radius is smaller than the atomic radius of the element with one fewer protons,
but my +1 ionic radius is larger than the +1 ionic radius of the element with one fewer protons. Of the
two elements in my group that have biological importance, I am the one with higher electronegativity.
8. Another method to predict bond types (besides using electronegativity differences) is to compare the atomic
volumes (based on the ionic radii) of the cations and anions. Starting from the assumption that a bond is totally
ionic this approach looks at the polarizability of the anion and polarizing ability of the cation to assess how
much electron density is pulled into the region between the ions. Discuss this using the series of halides as
examples: NaF, NaCl, NaBr, NaI; and BeF2, BeCl2, BeBr2, BeI2. (Googling for 'Fajans rules' will get you more
information on this approach to describing bonds.)
5. (a) List those elements which commonly form molecules where the element has less than an octet of
electrons.
(b) List those elements where the element often has more than an octet of electrons in its compounds.
6. (a) Draw all possible canonical (resonance) forms for each of these species:
2
(i) NO2 (ii) CO3
(b) Draw a Lewis structure for methanol (CH3OH).
(c) Would you expect the CO bond in carbonate to be longer or shorter than the CO bond in CH3OH?
(d) Would you expect the bond energy for the CO bond in carbonate to be larger or smaller than for the CO
bond in CH3OH?
NUMERICAL ANSWERS
1. (a) 8, (b) 8, (c) 32, (d) 48, (e) 8, (f) 20
References: Blackman, et al. 'Chemistry': 5.5, 5.6. CHEM1031 and CHEM1051: 5.7
4. (a) What is meant by delocalization of electrons? Under what circumstances is this effect invoked?
(b) Delocalization of electrons occurs in the following molecules: SO3, O3.
Draw all possible canonical (resonance) forms for each of these species.
2 2
(c) Delocalization of electrons also occurs in CO3 . Sketch the valence orbitals on the atoms in the CO 3
ion showing how delocalized bonding originates.
CHEM1031/1051 only
6. In graphite, three of the four valence electrons from each carbon atom are involved in forming bonds from
overlapping sp2 orbitals. The fourth valence electron is involved in bonding. A single crystal of graphite
conducts electricity in the two dimensions which form the sheets, but not in the third dimension. Therefore
electrical conduction occurs within a sheet but not between sheets.
(a) Sketch the orbitals around a carbon atom in graphite and a neighboring atom, showing how orbital
overlap gives rise to and bonding.
(b) Are the electrons involved in bonding localized between pairs of carbons atoms?
(c) Which of these statements best expresses a theoretical explanation (implied above, but not stated) for the
conclusion that conduction occurs within a sheet but not between sheets?
(i) Delocalization of electrons in graphite takes place in two dimensions rather than three dimensions.
(ii) The distance between sheets in graphite is too large for electrons to move between the sheets.
(iii) bonds must be present for the conduction of electricity
(iv) sp2 hybridization gives rise to sheet structures.
(Adapted from Garratt et al. "A Question of Chemistry", Longman, 1999)
8. Use arrows-in-boxes diagrams to rank the species C2, C2, C2+ in order of
(a) increasing bond order,
(b) increasing bond energy, and
(c) increasing bond length.
Mole fraction tells you what fraction of the molecules in the solution are of one type which is the most fundamental
way of expressing the composition of a mixture. On the other hand molarity is the most useful measure of concentration
in the laboratory where solutions of a particular molarity are easy to prepare (dissolve a known number of moles of
solute in a volumetric flask and make up to the mark).
Ideal Solutions
The ideal gas model assumes there is no interaction between gas molecules, except for totally elastic collisions. In
liquids intermolecular forces are dominant, they cannot be ignored, so in an ideal solution the magnitude of the
interactions between the components of the solution are taken to be the same as that between the molecules of each
component. That is, if a solution of A and B is ideal, then the forces A --- A and B --- B are the same as that of A --- B.
On this basis, there should be no heat evolved or absorbed when A and B are mixed and the volumes of the two liquids
should be additive, i.e. x mL of A added to y mL of B should produce (x + y) mL of solution.
Just as no known gases are ideal, no solutions are ideal over all possible concentrations unless A and B are the same
substance. However, just as most gases behave as if they were ideal under certain conditions of pressure and
temperature so some solutions formed from two liquids closely approximate ideal behaviour over the whole
concentration range and most solutions approach ideal behaviour when the solution is dilute i.e. the concentration of
one component present is very small its mole fraction, X, is close to zero. Examples of solutions which behave as if
they were ideal over the whole concentration range (X = 0 to X = 1) are methanol and ethanol, benzene and toluene,
solutions of the liquid alkanes, CCl4 and SiCl4, i.e. solutions in which A and B are structurally similar. Benzene and
CCl4, which are not structurally similar but are both nonpolar, also form solutions which behave close to ideal over the
whole concentration range. Several properties of the ideal solution (such as vapour pressure, density) can be calculated
by averaging the properties of the two liquids.
Call the two volatile liquids A and B. ("volatile" means "has a measurable vapour pressure"). Let the vapour pressure
and that of pure B be P at the same temperature. The partial pressure of A above the solution is P ,
of pure A be PA B A
and that of B is PB. For a solution of A and B behaving ideally, the partial pressure of A is proportional to the mole
fraction of A in the solution:
PA = XA PA . (1)
nA
, the vapour pressure of pure A, X =
where PA A nA + nB and nA, nB are the amounts (moles) of A and B..
Similarly PB = XB PB
This empirical relationship was proposed by Raoult, it has been verified experimentally, and is known as
Raoult's Law. It is obeyed by ideal solutions.
Vapour
Pressure
of B
o
PB
PT Vapour
Pressure
of A
Po
A
P P
A B
How is the solution composition related to the vapour composition? If YA is the mole fraction of A in the vapour, then:
PA PA XA P A
YA = = = . (3)
PA + PB PT PT
since the pressure exerted by A in the vapour is directly proportional to the number of molecules of A in the vapour. If
> P as is the case for the two liquids in Fig. 1, it follows that from equation 3 that Y > X , that is, the vapour is
PB T B B
always richer in the more volatile component than is the solution. This is the basis of fractional distillation.
P
A
P
A P
B
0.00 Mole Fraction of A in Solution 1.00 0.00 Mole Fraction of A in Solution 1.00
1.00 Mole Fraction of B in Solution 0.00 1.00 Mole Fraction of B in Solution 0.00
operate between the molecules. If these forces were very weak compared to the strength of the forces between CH 3OH
molecules and between CHCl3 molecules these two liquids would be immiscible. Since, in this case, the forces between
the molecules of different kinds are weaker than those between molecules of the same kind, the escaping 'tendency' of
molecules of each liquid is increased. Except in dilute solution, the vapour pressure of the solution is higher than that
of either pure component, and such solutions boil at temperatures lower than those of either pure component.
The molality of B is defined as mol B per kg of A and nA = mA 1000/MA where mA is the mass of A in kg, and MA
is the molar mass of A, in g mol1 therefore:
nB nB MA
PA = PA = PA . (5)
mA 1000/MA mA 1000
That is the change in the vapour pressure of the solvent, A, (PA) is equal to the molality of B (nB/mA) multiplied by
the quantity PA M /1000 which depends only on the identity of the solvent A. Any property of a solution which
A
depends only on the choice of solvent and the concentration of the solute is known as a colligative property.
1. (a) Complete the following table by ticking the appropriate boxes to indicate the types of intermolecular forces
acting between molecules in each of the compounds.
F2 Cl2 Br2 I2
What is the origin of the forces between molecules of F 2, of Cl2, of Br2 and of I2? Suggest reasons for
the observed trend in the boiling points of these compounds in terms of this force of attraction.
(c) Consider the following series of substances.
2. (a) State clearly what is meant by hydrogen bonding; give two examples of substances where hydrogen
bonding occurs.
(b) Draw the hydrogen-bonded structures, if any, for the hydrogen-bonding interaction which could occur
between the following pairs of molecules:
(i) H2O and NH3 (iv) H2O and CH3CH3
(ii) CH3COOH and CH3COOH (v) H2O and CH3OCH3
(iii) H2O and CH3OH (vi) H2O and CH3NH2
4. (a) The compressibility factors of the following gases at 273K and at 1 atm are listed. Select the gas where the
intermolecular forces are exerting the greatest attraction between the molecules. Give reasons to support
your choice.
7. Calculate the vapour pressure above a solution of 250.0 g of sucrose (C12H22O11) in 800.0 mL of water at
298K. The vapour pressure and density of pure water under these conditions are 23.76 mm Hg and 0.997 g mL 1
respectively.
8. At 35 C the vapour pressure of pure chloroform (CHCl 3) is 0.359 atm and that of acetone (CH3COCH3) is
0.453 atm. A solution containing 1.0 mole of chloroform and 4.0 moles of acetone has a vapour pressure of
0.400 atm at 35 C.
(a) Calculate the expected vapour pressure of the solution at 35C, assuming ideal behaviour, and compare
this value with the measured value.
(b) Does this system show a positive or negative deviation from Raoult's Law?
1
9. The equilibrium vapour pressures, at 90 C, of pure chlorobenzene (molar mass, 112.6 g mol ) and pure
1
bromobenzene (molar mass, 156.9 g mol ) are 220 Torr and 100 Torr, respectively. These two liquids are
completely miscible to form ideal solutions.
(a) For a liquid mixture containing 33.8 g of chlorobenzene and 172.6 g of bromobenzene, at 90 C, calculate
(i) the mole fraction of each component in the liquid mixture,
(ii) the partial pressure of each component in the vapour which is in equilibrium with the liquid
mixture, and
(iii) the mole fraction of each component in the vapour.
(b) Illustrate on a suitable diagram how the vapour pressure of each component and the total vapour pressure
above a solution of chlorobenzene and bromobenzene will vary with the mole fraction of chlorobenzene
in the solution.
(i) On the diagram show clearly the total pressure when there are four times as many chlorobenzene
molecules as bromobenzene molecules in the solution.
(ii) What is the composition of the solution when there are equal numbers of molecules of each
component in the vapour phase?
11. The diagram below shows a self-assembled monolayer (SAM) of long-chain alkanethiol molecules deposited from
aqueous solution onto a gold surface. The molecules shown here are of two different chain lengths, CH 3(CH2)9SH
and CH3(CH2)11SH. The thiol (SH) group binds strongly to gold.
Look at this SAM and identify as many different intramolecular and intermolecular interactions as you can.
Propose an explanation for the fact that the molecules spontaneously organise in an ordered way on the gold
surface. Can you think of another type of (commonly available) molecule which undergoes self assembly or self-
organisation? Below: a selfassembled monolayer of thiols attached to a gold surface.
Au
(Picture from P. Weiss, Penn. State U., http://stm1.chem.psu.edu/Pictures.html accessed February, 2009)
12. (a) What distinguishes a surfactant from other solutes when it is dissolved in water?
(b) What features of a molecule cause it to act as a surfactant?
(c) What is a micelle and under what circumstances do micelles form?
(d) How does micelle formation improve the effectiveness of surfactants as dirt and oil removers?
(e) Why does the fluid coating our lungs contain a very effective mix of surfactants?
NUMERICAL ANSWERS
5. (b) pO = 810 mm Hg, pH O = 355 mm Hg, ptotal = 1165 mm Hg
2 2
7. (a) 23.37 mm Hg
8. (a) 0.434 atm
9. (a) (i) 0.214 (ii) Pchlorobenzene = 47.1 Torr, Pbromobenzene = 78.6 Torr (iii) 0.375 (C) 0.625 (B)
(b) (ii) 0.313 (C) 0.687 (B).
1. (a) Write expressions for the equilibrium constants Kp and Kc, in terms of the partial pressures and
concentrations at equilibrium respectively, for each of the following reactions:
(i) 3 H2(g) + N2(g) 2 NH3(g)
(ii) CaCO3(s) CaO(s) + CO2(g)
(iii) 2 NH3(g) + H2S(g) (NH4)2S(s)
(iv) H2(g) + Cl2(g) 2HCl(g)
(b) For which, if any, of the reactions above, will the numerical values of Kp and Kc be equal?
4. When a mixture of carbon and carbon dioxide is heated, a reaction occurs to produce carbon monoxide:
C(s) + CO2(g) 2 CO(g)
The reaction (which occurs in blast furnaces used to produce iron) is endothermic.
Equilibrium mixtures of carbon, carbon dioxide, and carbon monoxide were subjected to the changes shown in
the following table. Complete the table by stating the effect each has on the amount of CO2 present and on the
value of Kp. Write 'increase', 'decrease', 'no change' or unpredictable'.
Effect on
Change
Amount of CO2 Kp
Decreasing volume
Adding CO(g)
Adding C(s)
Increasing temperature
(a) Calculate the value of the equilibrium constant Kc at the initial temperature.
CHEM1031/1051 only
6. Hydrogen sulfide decomposes at high temperatures according to the following reaction:
2H2S(g) 2H2(g) + S2(g)
For this reaction at 700 C Kc = 9.30 x 108. If 0.450 mol of H2S is placed in a 3.00 L container, what is the
equilibrium concentration of H2(g) at 700 C?
NUMERICAL ANSWERS
3
2. (a) 14.7; (b) 4.63 x 10
5. (a) [SO2] = ~0.70 M; [O2] = ~0.24 M; [SO3] = ~0.30 M ; Kc = ~0.77
(c) (i) [SO2] = ~0.68 M; [O2] = ~0.19 M; [SO3] = ~0.26 M ; Kc = ~0.77
(ii) [SO2] = ~0.63 M; [O2] = ~0.17 M; [SO3] = ~0.31 M ; Kc = ~1.4
6. 1.61 x 103 M
7. (a) 228
2. Complete the following table by writing equations which illustrate the acid/base nature in aqueous solution of
each substance:
Substance Equation
HCl
NH3
Na2CO3
CH3COOH
Fe3+(aq)
H2 O
2
HPO4
CN
HS
+ 1 1
[H ] /mol L pH [OH ] /mol L pOH
2
(i) 2.0 10
(ii) 3.20
2
(iii) 5.0 10
(iv) 4.60
6. (a) It is found that 0.20 M solutions of three potassium salts KX, KY and KZ have pH values of 7.0, 8.0 and
9.0 respectively. Arrange the acids HX, HY and HZ in order of increasing acid strength.
(b) The average pH of beer is 4.4. If the acidity is regarded as due only to the presence of dissolved CO 2 from
the fermentation process, calculate the concentration of the carbonic acid in the beer. (Acidity arising
from the second dissociation of carbonic acid may be neglected.)
(c) Lactic acid (CH3CHOHCOOH) is present in sour milk. What is the pH of a 0.100 M solution of lactic
acid? (pKa of lactic acid = 3.86)
9. What mass of potassium lactate should be added to 300.0 mL of 0.238 M lactic acid solution in order to produce
a solution with a pH of 4.00? (Lactic acid is a monoprotic acid, with formula CH 3CHOHCOOH, and having a
pKa value of 3.86.) (Assume no volume change on addition of solid.)
10. (a) (i) If 25.00 mL of 0.224 M ammonia were mixed with 50.00 mL of 0.138 M ammonium chloride,
what would be the pH of the final solution?
(ii) To what value would the pH change if 0.035 g of sodium hydroxide were added to this solution?
CHEM1031/1051 only
11. The value of the ion product for water (Kw ) varies with temperature. At 25 C Kw = 1.0 1014 (standard state
= 1 mol L1). Thus the pH of pure water at this temperature is 7.0. At higher temperatures Kw increases, so, for
example, at 60 C Kw = 9.3 1014. Thus at 60 C, the pH of pure water is 6.5 (verify this yourself). Does this
mean pure water is acidic at 60 C?
12. Ka for dichloroacetic acid (Cl2CHCOOH) is 3.3 102. Determine the pH of a 0.010 M solution of this acid by
(a) using an approximation to simplify the calculation, and
(b) without making any approximations. This will require solving a quadratic equation of the form
ax2 + bx + c = 0 using the general quadratic solution:
b b2 4ac
x=
2a
13. Determine the volume of 0.145 M hydrochloric acid which should be added to 250.0 mL of 0.096 M sodium
monohydrogenphosphate in order to produce a solution of pH 6.60.
14. Calculate the pH of a solution made by adding 10.0 cm3 of 5.0 107 M HCl to 90.0 cm3 H2O (hint: the trivial
answer to this is not correct).
NUMERICAL ANSWERS
3. (b) (i) 1.70; 5.0 1013; 12.30 (ii) 6.3 104; 1.6 1011; 10.80 (iii) 2.0 1013; 12.70; 1.30
(iv) 9.40; 4.0 10 10; 2.5 105
17
4. (c) 2.1 10
5. (a) 0.70 (b) 12.70 (c) 4.23 (d) 11.82 (e) 2.98 (f) 11.26
6. Ka for HY = 2 103, for HZ 2 105; (b) 3.5 103 M (c) 2.43
7. (a) 1.05 (b) 0.08 (c) 8.63 (d) 12.66 (e) 9.54
8. (a) 11.09 (b) 5.25 (c) 9.44
9. 12.6 g
10. (a)(i) 9.15 (ii) 9.27 (b)(i) 9.15 (ii) 9.40
12. (a) 1.7 (b) 2.1
13. 132 mL
14. 6.89
Although the International Union of Pure and Applied Chemistry (IUPAC) publishes standards for the presentation of
thermochemical data, there are many variations in the way such data is presented in textbooks and other compilations.
A statement of the conventions used should always accompany any set of data, e.g. see the detailed preface to Table 5
of SI Chemical Data (6th edition) to see the conventions adopted in that table.
1,
You should also note any information given in table headings such as units, e.g. fHo is given in kJ mol while Cop is
1 1
in J K mol . Another example: values of fHo in Table 6A are for the standard enthalpy of formation of the gaseous
substances, even though many of the substances are not gases under ambient conditions.
Standard States
In the context of thermodynamics a substance is in its standard state if it is pure (i.e. unmixed with any other substance)
and at a pressure of exactly 1 bar. The definition of standard state does not include a standard temperature, however the
temperature must be reported with any thermodynamic data. You will most often use data for 25 C. The adoption of 1
bar as the pressure used to define the standard state was made in 1994; prior to that a pressure of 1 atmosphere was used
(1 atm = 1.013 bar). A pressure of 1 atm is still used in defining normal boiling points (and other 'normal' phase
transition temperatures).
The standard reference state of an element is the stable phase under standard conditions, e.g., the standard reference
state of oxygen at 25 C and 1 atm is O2(g). This definition also allows for elements which can exist in several
allotropic forms (e.g. carbon can exist as diamond, graphite etc.) by including the specification of one allotrope (the
most stable, with one exception) in the standard state (for carbon the standard state is graphite; for phosphorus the
standard state is the white allotrope, which is not the most stable, but the most readily prepared in a pure form).
Thermodynamic properties can be calculated, but perhaps not measured, for substances in any of the three states solid,
liquid, gas even if the substance is not stable in that state, e.g., Cl(g) at 25C and 1 atm, or N2(s) at 25 C and 1 atm.
The standard enthalpy of formation of a substance in a given state is the enthalpy change associated with the formation
of 1 mole of the substance in that state from its constituent elements in their standard reference states. By this
definition fHo for any element in its standard reference state is zero. See tables 5 and 6A, 6B in SI Chemical Data.
3
e.g. for CaCO3: Ca(s) + C(graphite) + O2(g) CaCO3(s) fHo = 1207 kJ mol1
2
Other Standard Enthalpy Changes
The standard enthalpy of formation of a substance is significant because it provides a convenient way to calculate the
enthalpy change for chemical reactions involving that substance (using Hess' Law). Other generic processes or reactions
may be important because they reveal trends in properties of substances or are relevant to industrial or laboratory
processes. Note that the following named enthalpy changes may refer to particular states of the reactants and
products. The relevant information on these conditions is given in the preface to the data table or in table headings. The
table numbers refer to the sixth edition of SI Chemical Data.
Enthalpy change for the complete combustion of 1 mole of the substance in its stable form at 1 atm and 25C unless
otherwise specified, the final products being CO2(g) and H2O(l)
7
e.g. C2H6(g) + O2(g) 2 CO2(g) + 3 H2O(l) cHo = 1560 kJ mol1
2
Molar Heat (Latent Heat) of Melting or Fusion, fusHo Tables 5 and 13.
Enthalpy change for the transition solid liquid, commonly at the normal melting point temperature.
e.g. Al(s) Al(l) fusHo = 11 kJ mol1 at 660C (normal m.p.)
Enthalpy change for the transition liquid vapour at 25C and 1 atm.
e.g. for benzene: C6H6(l) C6H6(g) vapHo = +34 kJ mol1
Enthalpies of vaporization are sometimes given at conditions different from those above, e.g., at the normal boiling
point Table 13.
e.g. Ca(l) Ca(g) at 1484C (b.p.) vapHo = 151 kJ mol1.
Enthalpy change for the formation of cations from gaseous atoms, at 25C.
M(g) M+(g) + e first ionization enthalpy, Tables 14 and 15.
Mn+(g) M(n+1)+(g) + e (n+1)th ionization enthalpy, Table 14.
The energy change when electrons are added to gaseous atoms to form gaseous anions. Tabulated values are H at
25C for a process such as:
Cl(g) + e Cl (g) H = 355 kJ mol1
Enthalpy change for the dissociation of 1 mole of the substance in its crystalline state to its constituent gaseous ions.
+
e.g. LiBr(s) Li (g) + Br (g) H = 818 kJ mol1
Note that some texts define lattice enthalpy for the reverse process (gaseous ions to the crystalline solid).
Enthalpy change at 25C for the disruption of 1 mole of bonds in the reaction
gaseous molecules gaseous atoms.
e.g. CCl4(g) C(g) + 4 Cl(g) H = 4 Bond Enthalpy (C-Cl). Thus: BE(C-Cl)H = 327 kJ mol1.
The capacity of a substance equals the amount of heat required to raise the temperature of a given amount of that
substance by 1 K (or 1 C). If the amount of substance is 1 g the heat capacity is sometimes referred to as the specific
heat capacity e.g., the specific heat capacity of Cu(s) is 0.39 J K1 g1. Molar heat capacities (Tables 5 and 6A) refer
to 1 mole of the substance; e.g., the molar heat capacity of Cu(s) is 24 J K1 mol1.
Heat capacities describing temperature changes at constant volume are generally different from those at
constant pressure, especially for gaseous substances. The heat capacities listed in SI Chemical Data are for changes at
constant pressure and therefore relate to enthalpy changes.
Heat capacities are also weakly dependent on the temperature of the substance, so that accurate calculations for large
temperature changes require integration rather than simple multiplication of (heat capacity) temperature difference.
1
2. (a) A calorimeter, with calorimeter constant 7.31 J K , was used to measure the heat of reaction for mixing
+
100.0 mL of 0.100 M Ag with 100.0 mL of 0.100 M Cl . The temperature change was +0.770 K for the
1 1 3
200.0 g of solution (specific heat capacity = 4.35 J K g , density = 1.00 g cm ) and the calorimeter.
(i) What is the reaction occurring in the calorimeter?
(ii) How much heat was absorbed by the calorimeter?
(iii) How much heat was absorbed by the solution?
(iv) How much heat was released by the reaction?
(v) What is the heat of reaction per mole of product formed?
(b) High quality coal (anthracite) is almost pure carbon. The combustion of carbon to carbon dioxide
releases 393 kJ per mol of carbon burnt. If 1.000 kg of anthracite is burnt:
(i) How much heat is released?
(ii) How much ice (in kg) at 273 K could be melted to give water at 273 K using the heat in (i)?
(iii) How much ice at 273 K could be melted to give water at 100 C using the heat in (i)?
(iv) How much ice at 273 K could be melted to give steam at 373 K using the heat in (i)?
4. By using appropriate data from SI Chemical Data, calculate the standard enthalpy change and internal energy
change associated with each of these reactions at 25 C:
(a) CaCO3(s) CaO(s) + CO2(g)
(b) CH3CH2CH2OH(l) + 9/2 O2(g) 3 CO2(g) + 4 H2O(l) (CH3CH2CH2OH is propan-1-ol)
6. For the addition of chlorine to ethene to produce 1,2-dichloroethane: C2H4(g) + Cl2(g) C2H4Cl2(g)
H H H H
Cl2 + C C H C C H
H H Cl Cl
determine H at 298 K, in two ways:
(a) from average bond enthalpies, and
(b) from standard enthalpies of formation.
7. Without consulting a table of standard molar entropies predict whether S will be positive or negative for each
of the following reactions:
(a) 2 CO(g) + O2(g) 2 CO2(g) (b) 2 H2(g) + O2(g) 2 H2O(l)
(c) 2 O3(g) 3 O2(g) (d) 2 NH3(g) N2(g) + 3H2(g)
(e) 2 Na(s) + Cl2(g) 2 NaCl(s) (f) H2(g) + I2(s) 2 HI(g)
8. (a) Under what conditions are (i) G and (ii) G equal to zero?
(b) For the reaction Fe2O3(s) + 3 C(s) 2 Fe(s) + 3 CO(g) calculate
(i) H and S at 298K
(ii) G at 1000 K, assuming H and S are independent of temperature over the range 298K to
1000 K.
(iii) Kp at 1000K for Fe2O3(s) + 3 C(s) 2 Fe(s) + 3 CO(g)
CHEM1031/1051 only
11. For each of the following thermochemical processes, write the appropriate name(s) and insert the H value for
the process.
(i) Ba(s) Ba(g) (v) O(g) + e (g) O (g)
+ 2
(ii) Ba(g) Ba (g) + e (g) (vi) O (g) + e (g) O (g)
+ 2+ 1
(iii) Ba (g) Ba (g) + e (g) (vii) Ba(s) + 2 O2(g) BaO(s)
1 2+ 2
(iv) O (g)
2 2
O(g) (viii) BaO(s) Ba (g) + O (g)
Apply Hess's Law, construct a Born Haber cycle to calculate the lattice enthalpy for barium oxide and compare
o 1
12. For the process H2O(l) H2O(g) G298 = 8.6 kJ mol . Calculate the vapour pressure of water under
standard conditions at 25 C.
14. Experiments have been performed in which the force required to extend the length of a single DNA molecule
has been measured (see for example the journal Science, 1996, vol 271, pp. 792794). If the force required to
extend the length of a DNA molecule is approximately 80 pN, calculate the mechanical work required to extend
the molecule from 15 m to 20 m in length. Calculate the work required to extend one mole of DNA molecules
from 15 m to 20 m in length.
15. Microorganisms can bring about the fermentation of sugars into ethanol, for example, glucose:
C6H12O6(s) 2C2H5OH(l) + 2CO2(g)
Use data from SI Chemical Data to calculate the standard enthalpy change for this reaction. You will need to
calculate the enthalpy of formation of liquid ethanol first.
16. (a) Explain the difference between the definitions of the thermodynamic standard state used in non-biological
applications and in biological applications.
(b) If a reaction does not have H+(aq) as a reactant or a product, will the value of G for the reaction be
different under biological standard state conditions compared to the value under nonbiological standard
state conditions?
NUMERICAL ANSWERS
2+ 3+
anode Fe Fe + e oxidation
1 +
cathode O + 2H + 2 e H2O reduction
2 2
_________________________________________
2+ 1 + 3+
Reaction 2 2 Fe + O2 + 2 H 2 Fe + H2 O overall
2
The product formed is hydrated iron(III) oxide, Fe 2O3.xH2O commonly known as rust.
Magnesium, zinc, manganese, aluminium, chromium and iron are corroded by pure water even in the absence of
oxygen. (Reaction 3)
2+
anode Mg Mg + 2e oxidation
cathode 2 H2O + 2e 2 OH
+ H2 reduction
___________________________________
Reaction 3 Mg + 2 H2O Mg(OH)2 + H2 overall
Tiny particles of soot, charcoal and some kinds of dust often act as corrosion centres and, in the presence of sea spray
or particles of salt, accelerate atmospheric corrosion in maritime areas. Many metals which form basic salts, e.g. copper
and lead, also corrode in the presence of moisture and carbon dioxide to form basic copper(II) carbonate
Cu(OH)2.CuCO3 (an insoluble green salt) and basic lead carbonate Pb(OH) 2.PbCO3 (white) respectively. Even the
presence of microorganisms can influence the rate of corrosion.
Differential aeration
Most of the cells discussed so far have metals in contact with oxygen and/or aqueous or moist surroundings. Another
type of electrochemical cell that may be produced is that in which a metal is in contact with different concentrations of
its ions. Differential aeration promotes corrosion by the formation of such concentration differences. For example, iron
in oxygenfree water is more electro-positive (shows a greater tendency to lose electrons) than is iron in water which
contains dissolved oxygen. Consequently, if the same piece of iron is in contact with both kinds of water an emf may
be produced over a period of time. The oxygen content of the water at the edge of the drop will be greater than that at
the centre of the drop (that is, there is differing oxygen supply at various parts of a potential corrosion site this is
called differential aeration) and the difference in concentration of iron(II) ions in these two regions does itself lead to
The thin layer of water at the edge of the drop has a higher concentration of dissolved oxygen than does the water in
contact with the metal at the drop centre because this region is more remote from the atmosphere. The metal becomes
cathodic at the perimeter of the drop and anodic (greater tendency to lose electrons) where there is less oxygen. Iron(II)
2+
ions (Fe ) pass into solution from the corroding anodic region and hydroxide ions are formed at the edge of the water
drop (see reaction 1). When the ions meet, Fe(OH)2 is formed and this is Cross-section of door
oxidized subsequently to rust (Fe2O3.xH2O), which acts as an impediment to
the supply of oxygen to the anode. Corrosion is accelerated. Motor car bodies
are particularly prone to this form of corrosion, usually as a result of poor
design and construction methods. The corrosion of a car door is illustrated in
the adjacent diagram. Car doors fabricated from sheet steel frequently have an
overlapping joint along the bottom. Moisture finds its way into the joints
(through leaks around the window) and a site of differential aeration is created.
The rust is seen as a series of holes in a line along the bottom of the door.
Another example of this type of corrosion is that shown when a rubber band is
placed around a piece of iron which is immersed in water after some time
joint
the rubber band appears to have cut its way through the piece of iron owing to
this type of corrosion. The oxygen content of the water beneath the rubber
band is much less than that in the rest of the water. Corrosion of the iron beneath the rubber band is accelerated and so
the band can move relatively freely through the piece of metal as the iron below it is worn away.
The physical nature and solubility of the corrosion product in protection against corrosion.
Many of the oxide films formed are insoluble in water and so provide a protective film against further corrosion. Those
oxide films which are soluble in water, e.g. sodium oxide Na2O preclude the use of such metals as suitable for
corrosion prevention since they are water soluble (and indeed the metal itself reacts rapidly with water). In some cases,
chemical reaction with the medium may form a different insoluble product which then becomes a protective film,
e.g. PbSO4 film protects metallic lead from further corrosion by sulfuric acid. If the corrosion product is soluble,
disintegration of the metal will proceed. For example, lactic acid is formed in sour milk and its iron salts are very
soluble.
The physical nature of the oxide film is an important factor in corrosion prevention. If a material is to be protected
from corrosion by depositing (electrolytically) a thin layer of another metal over the surface, then the oxide of the metal
Sacrificial anodes
When it is impossible or impracticable to alter the nature of the corrosion medium (e.g. oxygen, water, presence of
salts, acids, etc.) or to coat the metal (e.g. with another metal as in galvanising or plating or by the application of paint,
lacquer, etc.), one method of corrosion prevention is by the use of a sacrificial anode.
Sacrificial anodes are made from metals which, in contact with 1 M solutions of their ions, have a smaller (i.e. more
negative) standard reduction potential than is that of the metal/metal ion system whose metal they are intended to
protect. For example, magnesium bars are bolted along the sides of ships to protect the iron hull; magnesium rods are
inserted into domestic water boilers to prevent rusty water being formed; magnesium sheets are buried near iron
pipes to protect the pipe. In each of these cases, the magnesium eventually is corroded away (i.e. is oxidized) and the
bars, rods, sheets, etc. of it are much cheaper and easier to replace than is the item they are protecting which is
composed of iron. In other words, the magnesium is sacrificed in the course of protecting the iron from corrosion.
For the iron pipe connected to a magnesium metal sheet, several electrochemical cells may be set up. These include
those represented by Reactions 1 and 2 above (the reactions to be suppressed here) and Reaction 3 (above) as well as
those shown below.
2+
anode Mg Mg + 2 e oxidation
1 +
cathode O + 2 H + 2 e H2O reduction
2 2
____________________________________
+ 1 2+
Reaction 4 Mg + 2 H + O2 Mg + H2 O overall
2
Whether Reaction 3 or Reaction 4 proceeds depends very much on the soil conditions.
2+
anode Mg Mg + 2 e oxidation
2+
cathode Fe + 2 e Fe reduction
______________________________
2+ 2+
Reaction 5 Mg + Fe Mg + Fe overall
Reactions 3 and 4 would be expected to take place preferentially to Reactions 1 and 2 because magnesium has a greater
tendency to be oxidized than does iron. Hence the corrosion of iron is inhibited. Since the magnesium is connected to
the iron pipe, the iron(II) ions produced by Reaction 1 could be reduced back to the metal, according to Reaction 5,
and the pipe thereby protected from corrosion. The moist soil is an essential part of the cell because containing as it
does moisture and dissolved ions (in addition to the ions produced by Reactions 3 and 4) it acts as a salt bridge for the
cell represented by Reaction 5.
Zinc or chromium would be satisfactory to use instead of magnesium (ignoring the cost of the metals) because either
would act as a sacrificial anode.
If instead of using a magnesium sheet, a copper sheet was used, a potentially disastrous situation would exist. The pipe
would corrode very rapidly and a situation analogous to that described earlier (HMS Alarm) would prevail. The Cu
Element O N Hg Cl Cl Cl S S Cr Mn
Oxid. No.
3. By means of ion electron half equations, write balanced overall ionic equations for each of the following
reactions:
(a) copper metal reacted with dilute nitric acid solution to produce a solution of copper(II) nitrate and
nitrogen dioxide gas,
(b) ethanol was oxidized to ethanoic acid by acidified dichromate,
(c) acidified solutions of iodide and iodate ions were mixed, producing iodine,
4. (a) What is meant by 'standard reduction potential'? Under what conditions is it measured?
(b) Using SI Chemical Data, find standard reduction potentials for the following processes:
+ 2+
(i) MnO (aq) + 8H + 5e Mn +4H O
4 2
3+
(ii) Al + 3e Al
(iii) Cl (g) + 2e 2 Cl
2
2+
(iv) Mg + 2e Mg.
(c) Consider the four half-equations in (b):
(i) Which substance is the strongest reducing agent?
(ii) Which substance is the strongest oxidising agent?
(iii) Give an equation for the spontaneous reaction occurring in an electrochemical cell made from the
standard Mg and Cl2 couples.
(iv) Make a labelled drawing to represent this electrochemical cell. Mark on your drawing the
following features:
Anode, cathode, salt bridge, direction of electron flow, direction of movement of anions and
cations in the salt bridge, identity and concentrations of all chemical species in the system.
(v) Write the conventional cell diagram for this cell.
(vi) What is E, the standard cell potential for this cell?
7. (a) Find the standard emf for each of the following galvanic cells (represented using conventional cell
diagrams) and write the chemical equation for the reaction in the cell as written.
2+ 2+
(i) Fe | Fe || Cu | Cu
2+ +
(ii) Fe | Fe || Ag | Ag
2+
(iii) Sn | Sn || Br | Br2(l) | Pt
2+ 3+ 2+
(iv) Pt | Fe , Fe || Hg | Hg
2+ 2+
(v) Zn | Zn || Co | Co
+ 3 1 2+ 1
(b) Calculate the emf of cell (ii) above, when [Ag ] = 10 mol L ; [Fe ] = 2.0 mol L and
temperature 25 C.
8. Electrolytic cells containing as electrolytes zinc sulfate, silver nitrate and copper(II) sulfate were connected in
series. A steady current of 1.50 A was passed through them until 1.45 g of silver was deposited at the cathode of
the second cell.
(a) How long did the current flow?
(b) What masses of copper and zinc were deposited?
9. Give explanations for the following observations, including as many relevant chemical equations with
o
appropriate E values, as you can:
(a) Steel clips holding copper pipes against the brick wall of a house rust rapidly, but the copper pipes appear
CHEM1031/1051 only
10. (a) For a cell in which the reaction Zn(s) + Ni2+(aq) Zn2+(aq) + Ni(s) is occurring, use the Nernst
RT
equation: E = E lnQ to calculate:
nF
(i) Ecell when [Ni2+] = 0.05 mol L1 and [Zn2+] = 0.85 mol L1.
2+
[Ni ]
(ii) the ratio when the cell is "flat".
2+
[Zn ]
(b) A concentration cell is constructed from two half cells composed of the same materials but differing in
ionic concentration. In the case of a cell constructed from two Zn electrodes having 1.0 M Zn 2+ and
0.10 M Zn2+ respectively, determine which is the anode and which is the cathode, and calculate the Ecell
at 298K.
11. The amount of lactic acid produced in a sample of muscle tissue was analyzed by reaction with hydroxide ion.
The hydroxide ion was produced in the sample by electrolysis, where the cathodic reaction is:
2H2O(l) + 2e H2(g) + 2OH (aq)
The hydroxide ions produced react immediately with the lactic acid. An acid/base indicator was used to detect
the end-point. It required 115 s for a current of 1.56 102 A to reach the end-point. Calculate the mass of
lactic acid that was present in the sample of muscle tissue.
12. Assume a pH electrode responds to a change in [H+] exactly according to the Nernst equation (with n = 1). If the
concentration of H+ increases by a factor of 10, what will be the change in the potential of the pH electrode (at
298 K)? What change in pH does this correspond to?
13. (a) Calculate the Gibbs energy change for: 6CO2(g) + 6H2O(l) C6H12O6(s) + 6O2(g).
(b) Is the reaction in (a) spontaneous?
(c) How is it that plants can carry out the reaction in (a)?
(ii) 55 25
10 11
(b) Naturally occurring boron is composed of only two isotopes 5 B and 5 B with isotopic masses of
10.0129 and 11.00931 respectively. To account for the atomic mass of 10.811, what must be the
percentage abundance of each isotope?
1
3. One of the hydrides of boron has molar mass = 122.22 g mol and is 11.55 % by mass hydrogen. Determine its
molecular formula.
4. Balance the following equations the final equation should show the lowest whole number coefficients of
reactants and products.
(a) (NH4)2Cr2O7 Cr2O3 + N2 + H2O
(b) K + H2O KOH + H2
5. (a) Calculate the number of oxygen atoms that are contained in 1.10 moles of copper(II) sulfate pentahydrate.
(b) Determine the number of moles of chromium atoms in 25.0 g of sodium chromate.
(d) How many grams of methanol (CH3OH) must be added to 50.0 g water to make a solution containing
7. (a) Calculate the percentage composition, by mass, of each element in C2H5OH (ethanol).
(b) The composition of caffeine is 49.48 % carbon, 5.15 % hydrogen, 16.49 % oxygen, and 28.87 % nitrogen
by mass. The molar mass of caffeine is 194.2 g mol1. Determine the empirical formula and the
molecular formula of caffeine.
NUMERICAL ANSWERS
10
1. (b) 19.902 % 5 B;
3. B10H14
5. (a) 5.962 1024, (b) 0.154, (c) 80.64 g, (d) 88.89 g
6. (b) 917 g
7. (a) 52.1 % C, 13.1 % H, 34.7 % O , (b) molecular formula: C 8H10N4O2
3. Commercial "antacids" frequently contain oxides or carbonates which react with excess stomach acid, assumed
to be HCl. Each tablet of a certain antacid contains aluminium hydroxide (200 mg) and magnesium hydroxide
(200 mg). Assume the hyperacidity is due to HCl in the gastric juices, calculate the amount of acid neutralized
by each tablet. Express your answer as mL of 0.100 M HCl.
5. (a) The volume of a gas is 45.0 L at 25 C and 750 mmHg. What volume will it occupy at the same
temperature, but at 1.00 atm pressure?
(b) 500 mL of a gas at 10 C, exerts a pressure of 1.0 atm. What will be the pressure if the temperature is
increased to 50 C and the volume is kept constant?
(c) Calculate the molar mass of a gas if the gas has a density of 3.64 g L1 at 27 C and 772 mmHg.
6. Hydrogen molecules leak through a pinhole in the shell of a space vehicle at the rate of 2.1 107 mol hr1.
(a) How many molecules of hydrogen escape in 24 hours?
(b) Under the same conditions, at what rate do molecules of water vapour escape through the same hole?
NUMERICAL ANSWERS
1 (a) 1.08 mol L1, (b) 1.16 mol kg1, (c) 0.020
2 (a) (i) 4.358 g (ii) 1.249 g (iii) 15.80 g, (b) (i) 278 mL (ii) 20 mL
3. 146 mL
4. (a) (i) 967 mm Hg; (ii) XH = 0.276 (b) 123 k Pa; 37.4 % He
2
5 (a) 44.4 L, (b) 1.14 atm, (c) 88.3 g mol 1
6. (a) 3.0 1018; (b) 7.0 108 mol hr1;
NUMERICAL ANSWERS
1. (a) 5.09 1014 Hz, 3.37 1019 J; (b) 464 nm
6 1
2. 1.5233 10 m , 656.5 nm, 4.567 1014 Hz
2. In each of the following pairs, which would be the larger ion? Give a reason for your answer.
(a) K+ and Cl (b) Cl and Br (c) Cu+ and Cu2+
3. Using electronegativity values describe the bonding within the following compounds as ionic, polar covalent or
covalent:
NaBr, MgBr2, AlBr3, SiBr4, PBr3, SBr2, Br2
4. (a) Draw all possible canonical (resonance) forms for N2O which has the connectivity NNO.
(b) Label each atom in each of the resonance structures in (a) with their formal charge.
(c) Based on formal charges, decide which resonance structure(s) best represent the electron distribution in
N2O.
NUMERICAL ANSWERS
1. (a) 20, (b) 24, (c) 24, (d) 40
2. What is the hybridization of each of the carbon atoms in the following compounds:
(a) CH3CH=NH (d) CH3C CCHO
(b) CH3COOCH3 (e) cyclobutane
(c) CH3OCH3 (f) C6H6 (benzene)
2. F2(s), NF3(s) and H2O(s) are all molecular solids. Clearly explain what this means and indicate the type and
relative strengths of all intermolecular and intramolecular forces of attraction. Comment briefly on the expected
physical properties of molecular solids.
3. At 55C, acetone (CH3COCH3) has a vapour pressure of 738 mmHg and chloroform (CHCl 3) has a vapour
pressure of 638 mmHg. Which of these liquids has the higher normal boiling point? Why? What are you
assuming in making this prediction?
4. (a) Glycerol is a viscous, nonvolatile liquid at room temperature. Calculate the vapour pressure above a
solution of 150.0 g of glycerol (C3H8O3) in 700.0 mL of water at 298K. The vapour pressure and density
of pure water under these conditions are 23.67 mm Hg and 0.997 g mL1 respectively.
(b) At 20.0C the vapour pressure of pure methanol is 11.8 kPa and that of pure ethanol is 5.93 kPa. A
gaseous mixture of methanol and ethanol is cooled and compressed until the first drops of liquid form at
20.0C and a total pressure of 10.0 kPa. Assuming the liquid mixture behaves ideally, calculate the mole
fractions of methanol in:
(i) the liquid phase, and
(ii) the gas phase
NUMERICAL ANSWERS
1. (a) (i) 240 mm Hg (ii) 911 mm Hg
4. (a) 22.7 mm Hg (b) (i) Xmethanol, liq = 0.694 (ii) Xmethanol, gas = 0.818
Chemical equilibrium
1. (a) Write expressions for the equilibrium constants Kp and Kc, in terms of the partial pressures and
concentrations at equilibrium respectively, for each of the following reactions:
(i) 2H2(g) + O2(g) 2H2O(g)
(ii) 2HgO(s) 2Hg(l) + O2(g)
(b) For each of the reactions above write an expression which relates the values of Kp and Kc.
(c) If the partial pressure of O2 in equilibrium with a sample of HgO(s) at a particular temperature was
0.015 bar, what would be the value of Kp for reaction (ii) above at that temperature?
NUMERICAL ANSWERS
1. (c) Kp = 0.015
3
2. (a) 2.02 102; (b) 2.45 10
+ 1 1
[H ] /mol L pH [OH ] /mol L pOH
4
(i) 2.0 10
(ii) 1.30
3
(iii) 5.0 10
(iv) 5.60
3
4. (a) 7.84 g KCN is dissolved in water and the volume of the resultant solution is 450 cm . If the pH of the
solution is 11.3, what is the pKa of HCN?
NUMERICAL ANSWERS
2. (a) (i) 3.70; 5.0 1011; 10.30 (ii) 5.0 102; 2.0 1013; 12.70 (iii) 2.0 1012; 11.70; 2.30
(iv) 8.40; 4.0 109; 2.5 106
3. (a) 0.70 (b) 13.30 (c) 4.19 (d) 11.2
4. (a) 9.2 (b) 5 103 % (c) increased to 1.6 102 %
5. 4.67
Thermodynamics
1. A pack has been developed so that small amounts of food can be heated without the need to light a fire or burn
fuel. The researchers who designed the pack found that by mixing powdered magnesium metal with sodium
chloride and iron particles the following exothermic reactions would occur rapidly when water was added:
1
Mg(s) + 2 H2O(l) Mg(OH)2(s) + H2(g) H = 355 kJ mol
Thus, when water is poured into a porous pad containing the powdered magnesium mixture, heat is released.
This energy warms food contained in an adjacent sealed food pouch. Assume that the pack contains 0.10 g of
powdered magnesium.
(a) Calculate the maximum amount of heat that can be released by adding water to the powdered magnesium.
(b) Calculate the minimum mass of water that must be added to release this amount of heat.
(c) The directions on the pack specify the addition of a certain volume of water. If 50 mL of water is added,
1 1
calculate its maximum rise in temperature, assuming a heat capacity of 4.2 J K g and a density of
1
1.00 g mL for all solutions.
2. By using appropriate data from SI Chemical Data, calculate the enthalpy change and internal energy change
associated with this reaction at 25 C: CuO(s) + H 2(g) Cu(s) + H2O(l)
3. When 2.50 g of ammonium chloride is dissolved in 100.0 g of water the temperature falls by 1.70 K. Calculate
1 1
the enthalpy of solution of ammonium chloride, assuming a heat capacity of 4.2 J K g and a density of 1.00
1
g mL for all solutions.
Element O N Cu Cl Cl S C C Mn
Oxid. No.
2. By means of ion electron half equations, write balanced overall ionic equations for each of the following
reactions:
(a) an acidified solution of oxalate ion was oxidized to carbon dioxide by permanganate ion,
(b) adding acid to a solution of sodium thiosulfate produced elemental sulfur and sulfur dioxide.
2+ 2+
3. The standard reduction potential for X | X is + 0.40 V and that for Y | Y is 0.40 V. What happens when:
2+
(a) a piece of X is placed in a solution of Y ?
2+
(b) a piece of Y is placed in a solution of X ?
(c) a piece of X is placed in 1 M HCl?
(d) a piece of Y is placed in 1 M HCl?
Give reasons for your answer in each case.
4. (a) Find the standard emf for each of the following galvanic cells (represented using conventional cell
diagrams) and write the chemical equation for the reaction in the cell as written.
2+ +
(i) Fe | Fe || Ag | Ag
2+
(ii) Sn | Sn || Br | Br2(l) | Pt
2+ 3+ 2+
(iii) Pt | Fe , Fe || Hg | Hg
5. (a) What is the difference between a galvanic (or voltaic) cell and an electrolytic cell?
(b) Calculate the mass of cadmium that may be deposited from a solution of cadmium sulfate by the passage
of a 1.02 ampere current for 2 hours 20 minutes.
NUMERICAL ANSWERS
4. (i) 1.24 V, (ii) +1.22 V, (iii) +0.08 V
5. 4.99 g.