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(a) Use Trouton's rule, Hvap(88Jmol-1K-1)Tbp, to estimate the enthalpy of vaporization of octane (b.p. 126).

(b) Use the form of the Clausius-Clapeyron equation below to estimate the vapor pressure of octane at the column temperature in Figure 24-9(70C)

In(P1P2)=-(HvapR)(1T1-1T2)

(c) Calculate the vapor pressure for hexane (b.p. 69C) at70C

(d) What is the relationship between solute vapor pressure and retention?

(e) Why is the technique called "gas chromatography鈥 if retained analytes are only partially vaporized?

Short Answer

Expert verified

a)Hvap35125.2Jmolb)P2=135.10mmHgc)P2=783.81mmHg

Step by step solution

01

 a) Enthalpy of vaporization

Given:Tbp=126C

Find: enthalpy of vaporization role="math" localid="1657772978189" (Hvap)of octane using the Trouton's rule

Hvap88Jmol.K.Tbp

Convert the given temperature to Kelvin (K):

Tbp=126C+273.15=399.15K

Compute the enthalpy of vaporization (Hvap)of octane using the Trouton's rule:

role="math" localid="1657773979789" Hvap88Jmol.K.399.15K35125.2Jmol

02

b) Vapor pressure of octane

The Clausius-Clapeyron equation to be used in the problem is shown below:

InP1P2=-HvapR1T1-1T2

where:

-P1=vaporpressureatT1(K)

-P2=vaporpressureatT2(K)

- Hvap= enthalpy of vaporization of the substance

-R=gasconstant8.314JmolK

Given:

- T1=Tbp=399.15K

- P1=1atm=760mmHg(the vapor pressure is equal to atmospheric pressure the boiling temperature)

-T2=70C+273.15=343.15K

- Hvap=35125.2Jmol

Find: P2= vapor pressure of octane at the column temperature70C

Substitute the given values to the Clausius-Clapeyron equation:

role="math" localid="1657774107541" In760mmHgP2=35125.2JmolK8.314Jmol1399.15K-1343.15KIn760mmHgP2=1.7273760mmHgP2=5.6256P2=135.10mmHg

03

c) poly (ethylene glycol)

Given:

-T1=70C+273.15=343.15K

-T2=Tbp=69C+273.15=342.15K

-P2atm=760mmHg

Find: P1=vapor pressure of hexane at70C

Use Trouton's rule to compute for the heat of vaporization:

Hvap88Jmol.K.Tbp88Jmol.K.342.15K30109.2Jmol

Substitute the given values to the Clausius-Clapeyron equation to compute for the vapor pressure at70C

InP2760mmHg=30109.2JmolK8.314Jmol1343.15K-1343.15KInP2760mmHg=0.0308P2760mmHg=1.0313P2=783.81mmHg

04

d), e)

d. The relationship between solute vapor pressure and retention is that as vapor pressure decreases, retention increases. In Figure 24-9 in the textbook, retention increases with boiling temperature. However, boiling temperature has an indirect relationship with vapor pressure (i.e., higher boiling point = lower vapor pressure).

e. The technique is called gas chromatography because it is a method used to analyze volatile compounds in the gas phase, although retained analytes are only partially vaporized. In gas chromatography, the sample components are dissolved in a solvent and the analytes are separated by vaporizing the mixture. The sample is then separated into two phases: mobile phase and stationary phase.

05

final answer

a)Hvap35125.2Jmolb)P2=135.10mmHgc)P2=783.81mmHg

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Most popular questions from this chapter

Here is a student procedure to measure nicotine in urine. A 1.00-mL sample of biological fluid was placed in a 12-mL vial containing 0.7gNa2CO3powder. After 5.00渭驳of the internal standard 5 -aminoquinoline were injected, the vial was capped with a Teflon coated silicone rubber septum. The vial was heated to 80cfor 20 min and then a solid-phase microextraction needle was passed through the septum and left in the headspace for 5.00min. The fiber was retracted and inserted into a gas chromatograph. Volatile substances were desorbed from the fiber at 250cfor 9.5min in the injection port while the column was at 60c. The column temperature was then raised to 250cat 25c/minand eluate was monitored by electron ionization mass spectrometry with selected ion monitoring at m/z 84 for nicotine and m / z 144 for internal standard. Calibration data from replicate standard mixtures taken through the same procedure are given in the table.

(a) Why was the vial heated to 80cbefore and during extraction?

(b) Why was the chromatography column kept at 60Cduring thermal desorption of the extraction fiber?

(c) Suggest a structure for m / z 84 from nicotine. What is the m / z, 144 ion from the internal standard, 5 -aminoquinoline?

(d) Urine from an adult female nonsmoker had an area ratio m / z .84 / 144=0.51 and 0.53 in replicate determinations. Urine from a nonsmoking girl whose parents are heavy smokers had an area ratio 1.18 and 1.32.

Find the nicotine concentration (渭驳/L)and its standard uncertainty in the urine of each person.

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(b) What approach from (a) would be most cost effective (not involve a purchase)?

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