The pressure-volume work for an ideal gas can be calculated by using the expression;
The work can also be calculated from the pV plot by using the area under the curve within the specified limit. When an ideal gas is compressed reversibly or irreversibly from volume Vi to Vf, which of the following is correct?
A. wrev = wirrev
B. wrev < wirrev
C. wrev > wirrev
D. wrev = wirrev + pex. dV
When hydrochloric acid is added to the cobalt nitrate solution at room temperature, the following reaction takes place :
The solution is blue at room temperature. However, it turns pink when cooled in a freezing mixture. Based on this information, which of the following expression is correct for the forward reaction?
A. ΔH > 0
B. ΔH < 0
C. ΔH = 0
D. The sign of ΔH cannot be predicted on the basis of this information.
Enthalpy is a thermodynamic quantity equivalent to the total heat content of a system. It is equal to the internal energy of the system plus the product of pressure and volume.
Since the reaction shifts to backward direction on cooling, this means that the backward reaction is an exothermic reaction. Therefore, the forward reaction is an endothermic reaction and ∆H > 0. On the other hand, enthalpy cannot be zero(C option) because this above-given process is not isothermal(constant temperature).
Which of the following elements does not form hydride by direct heating with dihydrogen?
A. Be
B. Mg
C. Sr
D. Ba
In chemistry, a hydride is the anion of hydrogen, H−, or more commonly it is a compound in which one or more hydrogen centres have nucleophilic, reducing, or basic properties. In compounds that are regarded as hydrides, the hydrogen atom is bonded to a more electropositive element or groups.
All the elements except beryllium combine with hydrogen upon heating to form their hydrides, MH2.
2M + H2→ 2M+H- (M= Li, Na, K, Rb, Cs)
M’ + H2→ M’H2 (M’ = Mg, Ca, Sr, Ba, Ra)
Be cannot form hydride by this reaction because of the highest amount of ionization energy among alkali and alkali earth metals.
BeH2, however, can be prepared by the reaction of BeCl2 with LiAlH4
BeCl2 + LiAlH4→ 2BeH2 + LiCl + AlCl3
Which of the following species should be aromatic in character?
A.
B.
C.
D.
In 1931, German chemist and physicist Erich Hückel proposed a rule to determine if a planar ring molecule would have aromatic properties. This rule states that if a cyclic, planar molecule has 4n+2π electrons, it is aromatic. This rule would come to be known as Hückel's Rule.
From the above options A, B, C cannot be correct because of not being satisfied with huckle's rule.
Identify the pairs which are of isotopes?
A.
B.
C.
D.
Isotopes are variants of a particular chemical element which differ in neutron number, and consequently in nucleon number. All isotopes of a given element have the same number of protons but different numbers of neutrons in each atom.
Here, A is a mass number and Z is an atomic number of X(any element).
From the above notation, to be the pair of isotope Z should be similar. Only A and B have pairs of isotopes and one the other hand, C and D have different atomic number.
Electrophiles are electron seeking species. Which of the following sets consist of electrophiles only.
A. BF3, NH3, H2O
B.
C.
D.
In the set of A - NH3 and H2O are not the electrophiles as they have lone pair of electrons.
In the set of B – AlCl3, SO3, NO2+ are the electrophiles as AlCl3 is electron-deficient which tends to seek electron and later, SO3, NO2+ both are electrophiles.
In the set of C - NO2+, CH3+, CH3—C+=O are all electrophiles as because of positive charges.
In the set of D – all are not electrophiles as one of them have a negating charge which is a neutrophile indeed.
How many significant figures should be present in the answer of the following calculations?
Rule- For quantities created from measured quantities by multiplication and division, the calculated result should have as many significant figures as the measured number with the least number of significant figures.
Here, the least significant figure is of two. Therefore, there would be two significant figures present in the answer to the following calculations.
Complete the following reactions
(i)
(ii)
O2−2(aq) + 2H2O(l)→ H2O2(aq) + 2OH−(aq)
This is a Bronsted-Lowry acid-base reaction where peroxide ion acts as a base, accepting two H⁺ from water molecules. Alkaline and alkaline earth peroxides contain this ion, so they react with water to produce hydrogen peroxide.
2O2- (aq) + 2H2O(l) → H2O2(aq) + 2OH-(aq)
Give IUPAC name of the compound whose line formula is given below:
IUPAC name of the compound is according to the IUPAC rules. Here, the rules which will be applied are as follows-
Find and name the longest possible chain.
The numbering of the identified longest possible chain is based on the priorities.
The suffix in the name of a compound is based on the most priority group in that compound.
Based on these rules, IUPAC name of the compound given is 4-Methylhept-5-ene-2-one
Greenhouse effect leads to global warming. Which substances are responsible for the greenhouse effect?
The greenhouse effect is the trapping of the sun's warmth in a planet's lower atmosphere, due to the greater transparency of the atmosphere to visible radiation from the sun than to infrared radiation emitted from the planet's surface. Greenhouse gases are the substances responsible for the greenhouse effect.
The greenhouse gases in Earth's atmosphere are water vapour, carbon dioxide, methane, nitrous oxide and ozone.
Using molecular orbital theory, compare the bond energy and magnetic character of O2+ and O2– species.
According to molecular orbital theory electronic configurations of O2+ and O2– species are as follows
The higher bond order of O2+ shows that it is more stable than O2–. Both the species have unpaired electrons. So both are paramagnetic in nature.
Consider the reaction given below :
CaCO3 (s) → CaO (s) + CO2 (g)
Predict the effect of increase in temperature on the equilibrium constant of this reaction.
Given that
The standard enthalpy of formation or standard heat of formation of a compound is the change of enthalpy during the formation of 1 mole of the substance from its constituent elements, with all substances in their standard states.
To understand the type of reaction we need to calculate the enthalpy of the forward reaction.
[Standard enthalpy of formation of CaO + Standard enthalpy of formation CO2] – [Standard enthalpy of formation of CaCO3]
= [-635.1kj mol-1– 393.5kj mole-1]– [-1206.9kj mole-1]
= -1028.6kj mole-1 + 1206.9kj mole-1
= 178.3kj mole-1
This above reaction is an endothermic reaction.
If you increase the temperature, the position of equilibrium will move in such a way as to reduce the temperature again. It will do that by favouring the reaction which absorbs heat.
Hence, this above reaction would be in the forward direction while increasing the temperature.
pH of 0.08 mol dm–3 HOCl solution is 2.85. Calculate its ionization constant.
Given, pH =2.85 and C =0.08 mol dm-3
Now since HOCl is a weak acid its dissociation will be given as-
We know that;
pH = -log [H+]
-2.85 log [H+]
[H+] = antilog (-2.85)
[H+] = 1.41 × 10-3
We also know that, for a weak monobasic acid-
H+ =
[H+]2 =KaC (On squaring both sides)
Ka = 2.5 × 10-5
Hence the ionization constant of HOCl will be 2.5 × 10-5
Nitric acid is an oxidising agent and reacts with PbO but it does not react with PbO2. Explain why?
Pb valency in PbO is +2 and in PbO2 it is +4.
PbO is a basic oxide and simple acid-base reaction takes place between PbO and HNO3.
On the other hand in PbO2 lead is in + 4 oxidation state and cannot be oxidised further. Because if see lead’s electronic configuration [Xe] 4f145d106s26p2, maximum electron lead can give will be four and not more than that because d-orbital is full filled one and thus not letting it donate anymore. Therefore no reaction takes place. Thus, PbO2 is passive, only PbO reacts with HNO3.
2PbO + 4HNO3→ 2Pb (NO3)2 + 2H2O (Acid base reaction)
Calculate the strength of 5 volume H2O2 solution.
5 volume solution of H2O2 means that 1L of this H2O2 will give 10L of oxygen at STP
2H2O2(l) → O2 (g) + H2O(l)
2*34 g 22.4L at STP
68g
22.4L of O2 at STP is produced from H2O2 = 68g
5L of O2 at STP is produced from H2O2 = = 15.18g
Therefore, the strength of H2O2 in 5 volume H2O2 = 15.18g/L
According to de Broglie, matter should exhibit dual behaviour that is both particle and wave like properties. However, a cricket ball of 100g does not move like a wave when it is thrown by a bowler at a speed of 100km/h. Calculate the wavelength of the ball and explain why it does not show wave nature.
Given, mass (m) = 100g = 0.1 kg
Wavelength (λ) = 100 km/h = m/s = 27.78 m/s
According to the de Broglie equation, λ =
Where λ is wavelength,
h is Planck's constant, h = 6.626 10-34 Js
= 6.626 10-34 Kgm2s-1
m is the mass of a particle, moving at velocity v.
Substituting the values, λ = m
λ = 2.385 10-34 m
Since, the wavelength is very small due to large mass of ball therefore, wave nature was not observed and ball of 100g does not move like a wave when it is thrown by a bowler.
Explain why nitrogen has positive electron gain enthalpy whereas oxygen has negative; although first ionisation enthalpy of oxygen is lower than that of nitrogen. Justify your answer.
The outermost electronic configuration of nitrogen is 1s22s22p3.
Nitrogen has stable half filled configuration and therefore it has no tendency to accept electron therefore, energy has to be supplied in order to add an electron to it. Thus, nitrogen has positive electron gain enthalpy.
On the other hand, the outermost electronic configuration of oxygen is 1s22s22p4. It does not have half filled or fully filled stable configuration so it shows tendency to accept electron and thus, it has negative electron gain enthalpy.
Although first ionisation enthalpy of oxygen is lower than that of nitrogen because O has 4 electrons in 2p subshell and it can lose one electron to acquire half filled stable electronic configuration and therefore, it has low ionization enthalpy. On the other hand N already have stable half filled electronic configuration so it would not readily lose its electron and thus, N has higher ionisation enthalpy than O.
Write Lewis structure of the following compounds and show formal charge on each atom.
HNO3, NO2, H2SO4
Formal charge = valence electrons- (lone pair electrons + 1/2 bounded electrons)
(i) Formal charge calculations:
For N: 5 – 1/2 (8) = +1
For O: 6 – 6 – 1/2 (2) = -1
(ii) Formal charge calculations:
For N: 5 – 1/2 (8) = +1
For O without H: 6 - 6 - (1/2)2 = -1
For O without H on left side of N:6-4-1/2 (4)= 0
For O with H: 6 - 4 - (1/2)4 = 0
(iii) Formal charge calculations:
For S: 6 - (1/2)8 = +2,
For O without H: 6 - 6 - (1/2)2 = -1,
For O with H: 6 - 4 - (1/2)4 = 0.
Although heat is a path function, even then heat absorbed by the system under certain conditions is independent of path. What are those conditions? Explain.
Those conditions are constant volume and constant pressure. This can be explained as given below-
By first law of thermodynamics:
qv = ∆U + (–w)
qv = ∆U + p∆V (since, –w = p∆V)
∆V = 0 because volume is constant.
qv = ∆U + 0
Therefore, qv = ∆U = change in internal energy
Now, At constant pressure
qp = ∆U + p∆V
Also, ∆U + p∆V = ∆H
Therefore, qp = ∆H = change in enthalpy.
Thus, at constant volume and constant pressure heat change is state function because it is equal to change in internal energy and change in enthalpy respectively which are state functions and they are independent of path.
The solubility product of Al(OH)3 is 2.7 × 10–11. Calculate its solubility in g L–1 and also find out pH of this solution. (Atomic mass of Al is 27 u).
Let S be the solubility.
Initially, assume 1 mole of Al(OH)3 was present. From which S moles of it was dissolved to give S and 3S moles of Al3+ and 3OH- respectively. This can be understood from the following equation.
Given, = 2.7 × 10-11
We know,
= [Al3+][OH-]3
= (S)(3S)3 = 27S4
S4 = = 1 ×
S = 1 × 10-3 mol L-1
Molar mass of Al(OH)3 = 27 + 163 + 13 = 78 g/mol
Solubility of Al(OH)3 in g L-1 = 1 × × 78 g/L
= 78 × = 7.8 × 10-2 g L-1
Hence, solubility of Al(OH)3 is 7.8 × 10-2 g L-1.
Now to find pH of the solution:
From above equation,
[OH-] = 3S = 3 × 1 × = 3 ×
We know,
We also know, pH + pOH = 14
Therefore, pH of the solution is 11.47
Calculate the oxidation number of each sulphur atom in the following compounds:
(a) Na2S2O3 (b) Na2S4O6
(Oxidation no. of every atom is underlined by red.)
(a) Na2S2O3
(b) Na2S4O6
Calculate the oxidation number of each sulphur atom in the following compounds:
(a) Na2S2O3 (b) Na2S4O6
(ii) Will the reactivity of both the isotopes of hydrogen be the same towards oxygen? Justify your answer.
(Oxidation no. of every atom is underlined by red.)
(a) Na2S2O3
(b) Na2S4O6
(ii) The reactivity of isotopes of hydrogen is not same towards oxygen because of their different bond dissociation enthalpy. Deuterium and tritium have higher bond dissociation enthalpy than hydrogen thus their reactivity is also low.
(i) Beryllium sulphate and magnesium sulphate are readily soluble in water whereas the sulphates of barium, calcium and strontium are only sparingly soluble. Explain.
(ii) Why is the temperature maintained around 393 K during the preparation of plaster of paris?
(i) Beryllium sulphate and magnesium sulphate are readily soluble in water whereas the sulphates of barium, calcium and strontium are only sparingly soluble because as we move down the group the solubility of sulphates decreases.
On moving down the group the lattice dissociation enthalpy and hydration enthalpy both decreases but the decrease in hydration enthalpy is more than that of lattice dissociation enthalpy. So water molecules are not able to break the metal sulphate bond and thus on moving down the group the sulphates become less soluble.
(ii) The temperature is maintained around 393K during the preparation of plaster of paris because at a temperature higher than 393K the whole water of crystallisation is lost and the result anhydrous CaSO4 formed is called dead burnt plaster as it loses the properties of setting of water.
2CaSO4. H2O → 2CaSO4 + H2O
(Plaster of pars) (Dead burnt plaster)
Give the reactions involved in the preparation of propane from the following :
(i) CH3—CH = CH2
(ii) CH3 CH2 CH2 Cl
(iii) CH3 CH2 CH2 COO– Na+
(i) Propene can be converted to propane by hydrogenation that is addition of H2 in the presence of Ni/Pd catalyst.
CH3—CH = CH2→ CH3CH2CH3
(propene) (propane)
(ii) Alkyl halides (except fluorides) on reduction with zinc and dilute hydrochloric acid give alkanes.
CH3 CH2 CH2 Cl → CH3CH2CH3 + HCl
(propane)
(iii) Sodium salts of carboxylic acids on heating with soda lime (mixture of sodium hydroxide and calcium oxide) give alkanes containing one carbon atom less than the carboxylic acid. This process of elimination of carbon dioxide from a carboxylic acid is known as decarboxylation.
CH3 CH2 CH2 COO– Na+ + NaOH → CH3CH2CH3
(propane)
Assertion (A) : The first ionization enthalpy of alkali metals decreases down the group.
Reason (R) : Increase in number of orbitals increases the shielding effect which outweighs the increasing nuclear charge, therefore, the removal of outermost electron requires less energy on moving down the group.
A. A and R both are correct but R is not the explanation of A.
B. A is false but R is correct.
C. A and R both are correct and R is the correct explanation of A.
D. A and R both are incorrect.
C. A and R both are correct and R is the correct explanation of A.
The first ionization enthalpies of the alkali metals are considerably low and further decrease down the group.
This is because the effect of increasing size due to increase in no. of orbitals outweighs the increasing nuclear charge, and the outermost electron is very well screened from the nuclear charge. Thus, it becomes easy to remove an electron from outermost orbital while moving down the group and this is the reason of decreasing ionisation enthalpy.
Assertion (A): Nitration of benzene requires the use of concentrated sulphuric acid and nitric acid.
Reason (R): The mixture of acids produces the electrophile for the reaction.
A. A and R both are correct but R is not the explanation of A.
B. A is false but R is correct.
C. A and R both are correct and R is the correct explanation of A.
D. A and R both are incorrect.
C. A and R both are correct and R is the correct explanation of A.
A nitro group can be introduced into the benzene ring by heating benzene with a mixture of concentrated nitric acid and concentrated sulphuric acid which is called nitrating mixture.
This nitrating mixture forms a very good electrophile called nitronium ion and then it attacks on benzene ring to form nitrobenzene.
Assertion (A) : Ozone is destroyed by solar radiations in upper stratosphere.
Reason (R) : Thinning of ozone layer allows excessive UV radiations to reach the surface of earth.
A. A and R both are correct but R is not the explanation of A.
B. A is false but R is correct.
C. A and R both are correct and R is the correct explanation of A.
D. A and R both are incorrect.
B. A is false but R is correct.
The upper stratosphere consists of considerable amount of ozone (O3), which protects us from the harmful ultraviolet (UV) radiations coming from the sun. Ozone is not destroyed by solar radiations rather it is destroyed because of release of chlorofluorocarbon compounds (CFCs), also known as freons.
Due to CFCs ozone layer is depleting and allows excessive UV radiations to reach the surface of earth. CFCs mix with the normal atmospheric gases and reach the stratosphere. In stratosphere, they get broken down by powerful UV radiations, releasing chlorine free radical which then reacts with ozone and results in depletion of ozone.
CF2Cl2UV→ Cl. + F2Cl
Cl. + O3 → ClO. + O2
(a) Liquids can be considered as very dense gases. When a liquid phase changes to gas phase, the liquid and the gas phases are in equilibrium and a surface separates the two phases. This surface is visible if both phases are in equilibrium and are below critical tempertaure and pressure. However, it is possible to interconvert liquid and gas wherein two phases are never present together.
With the help of a well-labelled diagram show that CO2 gas can be liquified by changing the pressure and temperature without passing through the situation when both gaseous and liquid CO2 are at equilibrium.
(b) Arrange the following liquids in increasing order of their viscosities. Give reason for your answer.
Water, benzene, ethane-1,2-diol.
(a) Suppose gas is at point ‘A’ and temperature there is T1. Now, on increasing the temperature of the gas above critical temperature (Tc) keeping the volume constant, the gas will reach at point ‘F’ and consider there is temperature T2 and volume V1 with pressure p1.
Now on compressing the gas up to Volume V2. During this compression the pressure and volume of the gas will move along the curve FG and will reach at point G. Now, on
cooling the gas as soon as gas will reach the point ‘H’ located on isotherm of Tc, it will liquify without passing through equilibrium state. The gas will not pass through two phases because V2 of the gas is less than Vc i.e. molecules are closer to each other. Gas is at a higher pressure than critical pressure. Cooling slows down the molecular motion and intermolecular forces can hold the molecules together.
(b) The given liquids in increasing order of their viscosities are as follows-
Benzene < water < ethane-1,2 diol
Ethane-1, 2-diol shows more extent of hydrogen bonding than water while in benzene hydrogen bonding is absent. This factor of hydrogen bonding makes the liquids viscous.
(a) Explain why :
(i) BCl3 is a Lewis acid.
(ii) Boric acid is a monobasic acid.
(b) Compound ‘A’ of boron reacts with excess NH3 to give a compound ‘B’. Compound ‘B’ on heating gives cyclic compound ‘C’. Compound C is called inorganic benzene.
(i) Identify compounds ‘A’, ‘B’ and ‘C’
(ii) Give the reactions involved in these processes.
(a)
(i) As BCl3 is an electron deficient molecule with B having only 6 electrons and therefore it acts as Lewis acid and can accept a pair of electron to complete its octet. This is done on the basis of Lewis concept which states that any electron deficient or positively charged species acts as Lewis acid.
E.g. : NH3 + BCl3→ H3N : BCl3
(ii) Monobasic acids are those which donate one proton to a base in an acid base reaction. Boric acid in water, accepts OH- ion acting as lewis acid and water releases H+ ions. So instead of donating one proton, it accepts one pair of electron and thus it is a monobasic acid and the reaction is as follows:
B(OH)3 + H2O → H+ + [ B(OH)4]-
(b)
(i) A = B2H6 B = B2H6.2NH3 C=B3N3H6
B2H6 reacts with excess NH3 to give B2H6.2NH3 which is formulated as [BH2(NH3)2]+[BH4]-. This on heating gives B3N3H6 (borazine) which is called inorganic benzene.
(ii) Reactions involved in these processes are-
3B 2H6 +6NH3 → 3[BH2 (NH3 )2 ]+ [BH4 ]- → 2B3N3H6 +12H
(a) Write two important differences between inductive and resonance effects.
(b) Give reasons to explain the following observations:
(i) Carbon number ‘2’ in CH3CH2Cl has more positive charge than that in CH3CH2Br.
(ii) CH3–CH = CH–CH = CH2 (I) is more stable than CH3–CH = CH–CH2–CH = CH2 (II).
(a)
(b)
(i) Carbon number ‘2’ in CH3CH2Cl has more positive charge than that in CH3CH2Br because Cl is more electronegative than Br and that’s why C-Cl bond is more polar than C-Br bond. Cl keeps the shared electron pair towards itself as it is more electronegative. So the carbon adjacent to Cl acquires more positive charge s compared to carbon adjacent to Br.
(ii) CH3–CH = CH–CH = CH2 (I) is more stable than
CH3–CH = CH–CH2–CH = CH2 (II) because I shows resonance effect whereas there is no conjugation in II. We already know that more the resonating structure more is the stability. I have 2 resonating structures and thus, it is more stable.
CH3–CH = CH–CH = CH2 ↔ CH3=CH - CH=CH - CH2