The goal of this forum is to make simplified chemistry so that everyone can unde rstand it.

Each of us can make a difference to our understanding of chemistry. O ur understanding of chemistry is not static but dynamic in nature. What we know in the past may not be good enough for today. We need to create and develop our knowledge of chemistry so that it is relevant for today context. Why does lead has higher melting point than tin, despite the fact that the melti ng point of group IV decreases as we go down? (not in the syllabus but just food for thought. Please note that the explanation here is not absolute truth) Ulex writes ... Any expectations that one has about chemical behaviour based on Periodic Table p atterns are necessarily empirical - in other words, the Table registers patterns without explanations. When used predictively, in the manner adopted by Mendelee v, explanations are not taken into account and anomalies occur. I often think th at Mendeleev was quite fortunate when he applied his predictive method to Group IV so successfully. If we consider what happens when a substance melts, we quickly realise that seve ral factors are involved. Basically, the particles of the solid must vibrate wit h increasing energy until they separate from each other. The amount of energy su pplied to do this depends on (a) the interparticle forces of attraction (b) the distance apart of the particles - the structure of the solid. If we assume metallic bonding in both tin and lead (tin has allotropes, which co mplicates matters), the inter-particle forces are those between the ions of the metal, and the electrons released into the inter-ionic space. You would expect t he ions to be 2+ in both cases, and lead ions to be larger than tin ions. Theref ore the attractive forces would be greater in tin than in lead. So far, the argu ment is in favour of tin having the higher melting point. Turning attention to structure, lead has the close-packed FCC structure, whereas tin has the much looser tetrahedral structure. This suggests a lower melting po int for tin. It appears that the second factor is more important than the first. Some support for this view is provided if you look at the data for boiling point s. The liquid metals have similar structures so the relative boiling points depe nd on interparticle forces and the boiling point of lead, 2013 K, is lower than that of tin, 2533 K. Is the term "inert pair effect" an escapism approach to describe the lower melti ng point of tin and lead and its compounds? CIE do not advocate student to use this term in explaining the abnormal behaviou r of tin and lead compounds. There is a more objective explanation by looking at the ionisation energy and the enthalpy of formation of the compounds. Supposing the enthalpy of formation is greater than the sum of the IE(first and second) b ut less than the sum of IE( first, second, third and fourth) then we would be ab le to predict the likely +2 oxidation state of tin and lead in its compound woul d most likely to be formed. does a +ve value of "Standard Enthalpy change of solution/dissolution" favors th e solubility of an ionic compound? Or is it the -ve value that favors it? Need to consider the combination of enthalpy of hydration and the lattice energy of the salt. A more negative enthalpy of solution the greater the solubility of the salt. Water need to penetrate between the ions held together by lattice str

ucture. This required energy and it must come from the energy of hydration which is exothermic. Therefore, the more exothermic the energy of hydration, the more soluble the salt. This is reflected by the solubility of the group 2 sulfate. Paper 43 Oct/Nov 2010 Question 2(c). Is there an assumption needed for the volum e of leach solution and the mass of leach solution in this question? The density of the leach solution was not given in this part of the question. The answer wa s expressed as a % of the leach solution. Is the student require to make assumpt ion in this type of question? My student could only express it in mol dm-3 in th e final answer. Is it correct to express two different quantities with different units ( mass of copper and the volume of leach solution) as a %? CIE Examiner reply: It looks to me as though one needs to assume either that the calculation is of % weight/volume(w/v) or that the solution has a density equal to that of water at 1 g/cm3 (which we tend to do, for example in calorimetry ca lculations using q = mc deltaT) 9701/42 May/June 2011 Question 5(c) Step 3 The marking scheme given for step 3 CH3COCl or (CH3CO)2O (aq. negates). 4-amino ph enol has two functional groups, namely -OH and -NH2 , attached to the ring and t hey are capable of reacting with CH3COCl. Why is CH3COCl chosen and not CH3COOH in this case to form paracetamol? CIE forum moderator. using CH3COOH would presumably result in an acid-base reaction between the basic phenylamine and the acid to give a salt instead of the ester also the involveme nt of the lone pair on the N in the delocalised ring makes it a poor nucleophile so the more powerful acylating agents are needed i.e. acyl chloride or acid anh ydride. Why the -OH isn t esterified as well I can t explain so will need to give that s ome more thought Another reply from chemistry forum participant. The mechanism involves nucleophiles OH and NH. Perhaps it is partly due to the n ucleophilicity of the N atom compared to the O atom. O is more electronegative t han N and less likely to give up it s lone pair as easily as nitrogen (this idea could also be used to explain why water is a weaker Lewis base than ammonia etc ....) In reality, a mixture of O- and N-acylated products would be formed...we can be easily misled to believe that the O- isomer does not form when it probably does as a minor product. In the majority of schemes in synthetic chemistry, we ignore all but the major product. Inert pair effect. There are various approaches of explanation on the inert-pair effect to account for the behavior of tin and lead elements. I would like to fi nd out whether this explanation that I read is acceptable to CIE. There is less shielding effect by the diffused inner orbital in tin and lead, namely, d and f orbital, hence making the nuclear attraction for the 2 outermost s-electrons to be held more strongly. Thus, there is less available electrons for forming bonds with chlorine or oxygen atom. The latest textbook explanation on inert-pair effect is based on chemical energe tics approach. CIE forum Moderator reply. A complicated topic and I will be interested to see o ther replies. Personally I would recommend the Chemguide site as a useful refere nce http://www.chemguide.co.uk/inorganic/group4/oxstates.html

9709/42 June/May2011 Question 2(b)(iii). The marking scheme give the following r emarks Other possible oxidants (Eo must be > +0.2V) include: S2O82, H2O2, Cl2, Br2, I2 and Ag+. No observations with the first three of these, but this should be stated explici tly, e.g. no colour change. Is chlorine water colourless so that there is no colour? Could chlorine water ap pear as green/yellow colour? CIE forum moderator reply. I think it s very unlikely any students will have seen chlorine water sufficient ly concentrated to give an obvious colour - but if an appropriate description wa s offered in an answer then I m sure it would be allowed as the intention is alw ays to credit correct chemistry.

Paper 43 Oct/Nov 2010 Question 5(b). For electrolysis to occur, the voltage applied to the cell must be at least as l arge as the E o cell, as calculated from standard electrode potentials. Use the Data Booklet to calculate E o cell for the production at the anode of (i) O2(g), ..................................................................... .................................................. (ii) Cl2(g). ................................................................... ................................................... Comment. There are two types of cell, namely electrochemical(battery) and electr olytic cell. They are not the same. It is important that you know the difference otherwise you are going to get confused. E0 values from Data Booklet are referr ed to electrochemical cell. Do not use E0 to calculate the electrolytic cell. Fo r electrolysis reaction, the electrolytic cell need an electrochemical cell or b attery to be placed across the electrolytic cell. The positive terminal of the electrochemical cell is connected to the titanium e lectode in the electrochemical cell. This is electrode where both Chlorine and o xygen may be produced or you may say that the chloride and hydroxide ions are di scharged. Remember that anode is where oxidation or loss of electrons are happen ing. In this question you are asked to find the least E0 of the electrochemical cell not the electrolytic cell. This means you have to ask this question. What then i s happening at the positive terminal of the electrochemical cell. Oxidation is a lso happening at the positive terminal of the electrochemical cell. Earlier in the question The equation for the cathode reaction is 2H2O(l) + 2e-> H2(g) + 2OH(aq) was given. Note that this is not the equation of th e standard hydrogen electrode. The solution is not neutral as OH- (aq) is presen t. The reaction taking place at the cathode of the electrolytic cell is the posi tive terminal of the electrochemical cell. Hence, the reaction is the same as th e cathode of the electrolytic cell. Similar explantion goes for the reaction happening at the negative terminal of t he electrochemical cell for both oxygen and chlorine that is written in (a). If you get a negative value then it is wrong. This is because the E0 of the batt ery cannot be negative. A negative value means that the battery is not working. Hence, the E0 of the electrochemical cell must be positive. Sir, for O/N 2008, Question no. 4 (a) (ii), Why is the answer 8? Can u explain?

What is mean by average molecule of the polymer? I don t really understand the q uestion. and for the same question, (b) (iii), how do we get the answer? why is it 4(c-c) - 2(c=c) ? For the same paper, question no. 6 (a), can we test using K MnO4 and say that the solution decolourised? Sir, for O/N 2008, Question no. 4 (a) (ii), Why is the answer 8? Can u explain? What is mean by average molecule of the polymer? I don t really understand the q uestion. and for the same question, (b) (iii), how do we get the answer? Answer:the monomer is CH2=CH(CH2CH2CH3). There are 5 Cs in this monomer. Since a verage no. of C in the polymer is 40. Hence there are 40/5 or 8 monomers per pol ymer. So does it mean that if they ask for average molecule of polymer, we take the to tal number of carbon contained in the polymer divide by the number of carbon in a monomer? (b) (iii), how do we get the answer? why is it 4(c-c) - 2(c=c) ? bonds broken: 4(CC) = 4 350 = 1400 kJ mol1 bond formed: 2 (C=C) = 2 610 = 1220 kJ mol1 ??H = +180 kJ mol1 C40H82 ??? C16H34 + 2 C12H24 The answer in MS is based on this equation. Your equation may not be this one an d your answer may be different from this one. C1----C16-C17-C18---C28-C29-C30 ---C40. Need to break C-C bond at these points C16-C17, C17-C18, C28-C29 and C29-C30 ass uming that the C=C bond is formed at C17-C18 and C29 and C30. Remember also a CH bond is formed at C16, and C28 and C-H bond is broken at C18 and C30. These ca ncelled off each other. For the same paper, question no. 6 (a), can we test using KMnO4 and say that the solution decolourised? No. You have to differentiate J and K. Acidified KMnO4 will give the same negati ve result with J and K. Question:So does it mean that if they ask for average molecule of polymer, we ta ke the total number of carbon contained in the polymer divide by the number of c arbon in a monomer? Ans: The number of monomer units is 8. But the number of C in each monomer is 5 and the average number of Carbons in the polymer is 40. The reason for mentionin g average is because of the different length of molecules in the polymer. Some a re longer, others may be shorter. Some may be 45, 40, or 35. Paper 4 Oct/Nov 2008 Q 9(a)(ii) My question: The examiner report mentioned (ii) Quite a few suggested the PCR re action, or something along the way, before electrophoresis. Marking scheme suggest ed (ii) these undergo electrophoresis OR are placed on agarose gel. Why is PCR n ot acceptable as a stage after treatment with restriction enzymes? In the recent Paper 42 June 2011 Q 7 (a) , PCR was mentioned as a stage before carrying out e lectrophoresis. The examiner report mentioned (a)Most candidates appreciated tha t the production of genetic fingerprinting starts with the extraction of DNA, fo llowed by the use of restriction enzymes before using the polymerase chain react ion. Which is the correct stage to mention after treatment with restriction enzy mes? CIE reply:

In 2008 it was an open-ended question and we discussed candidates answers and de cided that only answers which made sense in the context of the question and the syllabus would be permitted. This meant that we allowed PCR increasing the amoun t of DNA to investigate, in other words BEFORE treatment with restriction enzyme s. In 2011 the candidates had to place a list of stages in sequence and so we were rather tighter in the sequence since we had provided the information.