What is meant by positive & negative deviations from raoult’s law & how is the sign of ΔmixH related to positive & negative deviations from Raoult’s law?
Raoult’s law states that at a given temperature, the vapour pressure of a solution containing non volatile solute is directly proportional the mole fraction of the solvent.
Non ideal solutions shows positive & negative deviations from ideal behavoiur.
Non ideal solutions showing positive deviations from Raoult’s law- Consider a binary solution of two components A & B .If the A-B interaction in the solutions are weaker than A-A & B-B interactions in the two liquids forming the solution,then the escaping tendency of A & B types of molecules from the solution becomes more than from pure liquids.
As a result ,each component of solution has a partial vapour pressure greater than expected on the basis of Raoult’s law.This is called positive deviations from Raoult’s law,i.e PA> PA °xA & PB >PB°xB
ΔmixH is positive because energy is required to break A-A & B-B attractive forces.Hence endothermic process.
Non ideal solutions showing Negative deviations from Raoult’s law- in such solutions,the A-B interactions are stronger than A-A & B-B interactions .Due to stronger A-B interactions ,the escaping tendency of A & B types of molecules from the solution becomes less than from pure liquids. Consequently, each component of the solution has a partial vapour pressure less than expected on the basis of Raoults law. This is called negative deviations form Raoults law,i.e PA< PA °xA & PB B°xB
ΔmixH is negative because energy is released due to increase in attractive forces. Hence exothermic process.
A 5% solution (by mass) of cane sugar in water has freezing point of 271 K. Calculate the freezing point of 5% glucose in water if freezing point of pure water is 273.15 K.
A solution of glucose in water is labelled as 10% w/w, what would be the molality and mole fraction of each component in the solution? If the density of solution is 1.2 g mL-1, then what shall be the molarity of the solution?
Henry's law constant for CO2 in water is 1.67 x 108Pa at 298 K. Calculate the quantity of CO2in 500 mL of soda water when packed under 2.5 atm CO2 pressure at 298 K.
Calculate the mass of a non-volatile solute (molar mass 40 g mol-1) which should be dissolved in 114 g octane to reduce its vapour pressure to 80%.
The vapour pressure of pure liquids A and B are 450 and 700 mm Hg respectively, at 350 K. Find out the composition of the liquid mixture if total vapour pressure is 600 mm Hg. Also find the composition of the vapour phase.
Calculate the mole fraction of benzene in solution containing 30% by mass in carbon tetrachloride.
How many mL of 0.1 M HCl are required to react completely with 1 g mixture of Na2CO3 and NaHCO3 containing equimolar amounts of both?
H2S, a toxic gas with rotten egg like smell, is used for the qualitative analysis. If the solubility of H2S in water at STP is 0.195 m, calculate Henry's law constant.
An aqueous solution of 2% non-volatile solute exerts a pressure of 1.004 bar at the normal boiling point of the solvent. What is the molar mass of the solute?
Boiling point of water at 750 mm Hg is 99.63°C. How much sucrose is to be added to 500 g of water such that it boils at 100°C.Molal elevation constant for water is 0.52 K kg mol-1.
For the reaction R → P, the concentration of a reactant changes from 0.03 M to 0.02 M in 25 minutes. Calculate the average rate of reaction using units of time both in minutes and seconds.
Write the formulas for the following coordination compounds:
(i) Tetraamminediaquacobalt (III) chloride
(ii) Potassium tetracyanonickelate(II)
(iii) Tris(ethane-1,2-diamine) chromium(III) chloride
(iv) Amminebromidochloridonitrito-N-platinate(II)
(v) Dichloridobis(ethane-1,2-diamine)platinum(IV) nitrate
(vi) Iron(III) hexacyanoferrate(II)
(i) Write structures of different isomeric amines corresponding to the molecular formula, C4H11N
(ii) Write IUPAC names of all the isomers.
(iii) What type of isomerism is exhibited by different pairs of amines?
Why are solids rigid?
Write any two characteristics of Chemisorption.
Write the structures of the following compounds.
(i) α-Methoxypropionaldehyde
(ii) 3-Hydroxybutanal
(iii) 2-Hydroxycyclopentane carbaldehyde
(iv) 4-Oxopentanal
(v) Di-sec-butyl ketone
(vi) 4-Fluoroacetophenone
Which of the ores mentioned in Table 6.1 can be concentrated by magnetic separation method?
Why are pentahalides more covalent than trihalides?
Silver atom has completely filled d orbitals (4d10) in its ground state. How can you say that it is a transition element?
Glucose or sucrose are soluble in water but cyclohexane or benzene (simple six membered ring compounds) are insoluble in water. Explain.
The rate constant for a first order reaction is 60 s-1. How much time will it take to reduce the initial concentration of the reactant to its 1/16th value?
How the following conversions can be carried out?
(i) Propene to propan-1-ol
(ii) Ethanol to but-1-yne
(iii) 1-Bromopropane to 2-bromopropane
(iv) Toluene to benzyl alcohol
(v) Benzene to 4-bromonitrobenzene
(vi) Benzyl alcohol to 2-phenylethanoic acid
(vii) Ethanol to propanenitrile
(viii) Aniline to chlorobenzene
(ix) 2-Chlorobutane to 3, 4-dimethylhexane
(x) 2-Methyl-1-propene to 2-chloro-2-methylpropane
(xi) Ethyl chloride to propanoic acid
(xii) But-1-ene to n-butyliodide
(xiii) 2-Chloropropane to 1-propanol
(xiv) Isopropyl alcohol to iodoform
(xv) Chlorobenzene to p-nitrophenol
(xvi) 2-Bromopropane to 1-bromopropane
(xvii) Chloroethane to butane
(xviii) Benzene to diphenyl
(xix) tert-Butyl bromide to isobutyl bromide
(xx) Aniline to phenylisocyanide
Discuss briefly giving an example in each case the role of coordination compounds in:
(i) biological system
(ii) medicinal chemistry
(iii) analytical chemistry
(iv) extraction/metallurgy of metals
The time required for 10% completion of a first order reaction at 298 K is equal to that required for its 25% completion at 308 K. If the value of A is 4 x 1010 s-1. Calculate k at 318 K and Ea.
Alcohols are comparatively more soluble in water than hydrocarbons of comparable molecular masses. Explain this fact.
What is meant by 'disproportionation'? Give two examples of disproportionation reaction in aqueous solution.
Complete the following reactions:
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
Which is the last element in the series of the actinoids? Write the electronic configuration of this element. Comment on the possible oxidation state of this element.
The chemistry of the actinoid elements is not so smooth as that of the Lanthanoids. Justify this statement by giving some examples from the oxidation state of these elements.
Explain briefly how +2 state becomes more and more stable in the first half of the first row transition elements with increasing atomic number?
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