1.

The analysis of an organic compound gave the following data: (a) 0.4020g gave 0.6098g and 0.2080g of CO_(2) and H_(2)O respectively. (b) 1.01g by Kjeldahl method produced amonia whise was neutralised by 23.2mL of N/2HCl (c ) 0.1033g of the compound gave 0.2772g of BaSO_(4) (d) 0.1015g when vaporised in Victor Meyer's apparatus displaced 27.96mL of air at 15^(@)C and 766 mm pressure Calculate the molecular formula. (Aqueous tension at 15^(@)C=16mm)

Answer»

Solution :Moles of `C=1 xx` moles of `CO_(2)=1 xx (0.6098)/(44)= 0.0138`
Moles of `H= 2xx` moles of `H_(2)O = 2 xx (0.2080)/(18)= 0.0231`
Calculation of moles of N: m.e. of `HCl= 23.2 xx (1)/(2)=11.6`
`therefore` m.e. of `NH_(3)=11.6`
m mol of `NH_(3)=11.6`
Moles of `NH_(3)= (11.6)/(1000)= 0.0116`
`therefore` moles of `N =1 xx` moles of `NH_(3)=0.0116`
Moles of N in 0.4020g of compound `=(0.0116)/(1.01)xx 0.4020` =0.0046
Moles of `S=1 xx` moles of `BaSO_(4)= (0.2772)/(233.3)= 0.00119 (BaSO_(4)=233.3)`
Moles of S in 0.4020g of compound `=(0.00119)/(0.1033) xx 0.4020` = 0.0046
`therefore` mole of `C: H: N: S= 0.0138: 0.0138: 0.0046: 0.0046`
`=3:5:1:1`
Hence the empirical formula is `C_(3)H_(5)NS`
Calculation of molecular weight: PRESSURE due to dry AIR only `=766-16=750mm`
Volume of vapour of 0.1015g of compound at NTP `=(750 xx 27.96 xx 273)/(288 xx 760)=26.155mL`
`therefore` moles of vapour `=(26.155)/(22400)=0.00116`
Molecular weight `=("weight in grams")/("no. of moles") = (0.1015)/(0.00116)=86.97 ~~87`
Since empirical formula weight is also equal to 87, the molecular formula is `C_(3)H_(5)NS`


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