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1 Ethers are a class of organic compounds that contain an oxygen atom connected to two alkyl or aryl groups and have the general formula R-O-R. Ethers, such as diethyl ether (CH3CH2OCH2CH3), are commonly used as solvents for organic reactions due to the low level of reactivity and ability to dissolve both polar and non-polar compounds.

Below are examples of alicyclic ether Tetrahydrofuran and aromatic ether Furan.

(a) State the hybridization states of oxygen in Tetrahydrofuran and Furan. [2]

(b) For unbranched ethers, they share the same molecular formula with alcohols. Below are some of the physical properties of ethers and alcohols Molecular formula C2H6O C4H10O C7H8O Structure CH3CH2OH CH3CH2CH2CH2OH C6H5CH2OH Alcohol Boiling point 78C 118C 205C Solubility 100% 7.7% 4% Structure CH3-O-CH3 CH3CH2-OCH2CH3 C6H5-O-CH3 Ether Boiling point -24C 35C 154C Solubility 7.6% 6.9% 0%

(i) Calculate the difference in boiling points between the alcohols and ethers for the respective molecular formulae. Account for the trend of this difference. [3]

(ii) Tetrahydrofuran is found to be completely soluble in water. Suggest an explanation for this. [1] (c) Ethers can be synthesized in the following reaction.

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Tetrahydrofuran can be synthesized in the following reaction scheme, starting with a cyclic compound A with 6 carbon atoms.

(i) State the reagents and conditions needed for steps I and II. Hence, draw the structures of A, B and C. [5]

(ii) Write the equation representing step I. [1]

(iii)State the type of reaction in step III. [1] (iv)Step III of the reaction scheme is not satisfactory. Identify the problem and suggest an improvement to step III. [2] (v) In step III, the reaction proceeds via 3 parts: 1. Acid-base reaction between C and H2SO4. 2. Followed by an intra-molecular nucleophilic substitution reaction. 3. Finally by a loss of proton. Propose a mechanism for step III, showing clearly the movement of electrons using curly arrows. [3]

(d) In another ether synthesize reaction, CH3CH2CH2CH2OH and C(CH3)OH reacted separately with concentrated H2SO4 at 140C. It was discovered that the yield of ether differs greatly between the two reaction mixtures. State the compound which gives the lower yield of ether. Explain your answer. [2]

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2 Pangong Tso is a lake in the Himalayas situated at a height of about 4,350 m. The lake is due to the accumulation of rainwater that flowed down the mountainsides. Thus, the river contains many anions from the dissolved minerals such as F- and CO32-. Given that the concentrations of the two anions are: F- : 0.00100 mol dm-3 CO32-: 0.00200 mol dm-3 In order to separate the three anions from a 250 cm3 sample, you were told to add in 5 cm3 of Calcium Chloride solution and perform selective precipitation.

Given numerically: Ksp (CaF2) = 3.4 x 10-11 Ksp (CaCO3) = 3.8 x 10-9 (a) Suggest why Lead (II) Chloride is not favoured in use to precipitate the anions. [1]

(b) (i) Calculate the minimum concentration of Ca2+ required for the first trace of CaF2 and CaCO3 to be precipitated from the mixture. [2] (ii) Using your answer to (b)(i), explain which compound will be precipitated first. [2] (iii)Given that the maximum amount of A is precipitated when the first trace of B appears, calculate the concentration of Ca2+ required to precipitate the maximum amount of A. [4] (where A and B are representation of the compounds in (b) )

(iv)Briefly describe the steps to separate the two anions mentioned above. Quote appropriate values from your answer in (b)(iii). [2]

(v) Comment on the effectiveness of the selective precipitation reaction above. [1]

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Apart from the various types of anions found in the river, Platinum (II) salts are also observed to exist in the river.

(c) Platinum (II) salts can form square planar complexes. Successive addition of ammonia and hydrogen chloride to an aqueous platinum (II) salt produces, under different conditions, three compounds with empirical formula PtN2H6Cl2. Two of these, A and B, are non-ionic, with Mr = 211. A has a higher melting point but lower boiling point than B. The third compound, C, is ionic, having Mr = 422, and contains platinum in both its cation and anion. For each of A, B and C, suggest a structure that fits the above data. [3]

(d) Nichrome is an alloy of nickel (60%, by mass) with chromium and the alloy is useful because its electrical resistance changes very little with temperature. Explain, either in words or by unbalanced equations, the chemistry underlying the scheme below. [5]

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3 Dmitri Mendeleev invented the Periodic Table in 1869 to illustrate periodic trends in the properties of the then-known elements. The layout has been refined and extended as new elements have been discovered and new theoretical models developed to explain chemical behavior. This lead to further research into inorganic chemistry.

Inorganic chemistry is the branch of chemistry concerned with the properties and behavior of inorganic compounds as well as the study of repeating patterns in the physical and chemical properties of the elements in the periodic table.

(a) Sketch the graph of: (i) The 3rd ionization energy against elements graph for Period III elements. Hence, explain the shape of your graph. [5]

(ii) The electronegativity against elements graph for Period III elements. Hence, explain the shape of your graph. [3]

(b) Astatine (At) is a radioactive chemical element just below iodine in the Periodic Table. It is an important element in nuclear medicine (i) Predict the state and colour of Astatine at room temperature. [2]

(ii) Predict what happens when concentrated sulfuric acid is added to solid sodium astadide. Write equations for the possible reactions that take place. [4] (c) Diagonal relationships are similarities between certain pairs of diagonally adjacent elements in the second and third periods of the Periodic Table. An example would be Lithium and magnesium which both readily form their nitrides (as well as oxides) when burnt in air. Boron and silicon also show a diagonal relationship. For example, both BCl 3 and SiCl4 are readily hydrolyzed by water, whereas CCl4 does not. (i) Suggest a reason why lithium and magnesium show similar physical and chemical properties. [2]

(ii) Suggest a detailed reason for the difference in reactivity of BCl3, SiCl4 and CCl4 in water. [3] (iii)Considering the reaction of SiCl4, suggest a balanced equation for the hydrolysis of BCl3. [1]
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4 (a) The dry cell battery is commonly used in portable devices such as handphones and torch lights. It is a non-rechargeable battery, with zinc electrode coated with Zn(OH)2 and solid MnO2 coated on carbon electrode. During the discharging process, MnO2 is converted to MnO(OH) solid and hydroxide ions. The relevant redox half-equations are given in the table. Half-equation ( ( ) ) E/V +0.84 -0.76

(i) By means of a fully labeled diagram, describe how the value of the standard electrode potential of the Zn(OH)2/Zn system can be confirmed. [4] (ii) Write an overall equation for the discharging reaction and calculate the e.m.f. of the dry cell. [2] (iii)Suggest why it is unfavourable to use such batteries at high temperatures. [2] (iv)State one advantage of using this dry cell over a lead-acid accumulator. [1] (v) Explain why compounds of zinc are colourless. [2] (b) Besides their uses in dry cell batteries, compounds of manganese also have applications in organic chemistry. In particular, potassium manganite(VII) is a useful oxidizing agent. When methanol, HCHO, is reacted with acidified potassium manganite(VII), methanoic acid and manganese(II) ions are formed. The overall equation for the reaction is: ( ) ( ) ( ) ( ) ( ) ()

The methanoic acid formed can be further oxidized to carbon dioxide. At room temperature, the reaction proceeds at a slow rate. A few crystals of vanadium(III) nitrate are added to the mixture to speed up the reaction, which results from the formation of vanadate(IV) ions, VO2+, as an intermediate. (i) Calculate the oxidation number of carbon in HCOOH. [1]

(ii) Briefly describe the role of vanadium(III) ions in this reaction. [1]

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(iii)Referring to relevant values from the Data Booklet and from the data given, show how vanadium(III) ions act as a catalyst in th reaction. Include balanced equations in your answer. [2] (c) Using platinum electrodes, a current of 2.5A was passed through three beakers containing, respectively, aqueous silver nitrate, aqueous copper(II) sulfate and dilute sulfuric acid, connected in series. 0.40g of silver was deposited in the first beaker.

(i) Assign cathode or anode to the electrodes above, starting from left to right. [1]

(ii) Calculate the mass of copper deposited in the second beaker. [2]

(iii)Calculate the volume of hydrogen liberated at 17C and 1 atm in the third beaker. [2]

Copyright by Liu Ruoyang. All rights reserved. No part of this information may be reproduced or transmitted in any form or by means electronic or mechanical, including photocopying, recording or any information storage or retrieval system without prior permission from the author.