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Consider the chromatography of n-c12H26on a 25 m 脳 0.53 mm open tubular column of 5% phenyl鈥95% methyl polysiloxane with a stationary phase thickness of 3.0 渭尘and He carrier gas at 125潞C. The observed retention factor for n-c12H26is 8.0. Measurements were made of plate height, H, at various values of linear velocity,xm/s. A least-squares curve through the data points is given by

localid="1654864230381" H(m)=(6.010-5m2/s)/x+(2.0910-3s)xthecoefficientsofthevanDeemterequation,findthediffusioncoefficientofn-c12H26inthemobileandstationaryphases.Whyisoneofthesediffusioncoefficientssomuchgreaterthantheother?

Short Answer

Expert verified

Fromsubstitutingthevalueswegetthediffusioncoefficientofn-C12H26inmobilephaseis3.010-5m2sandthediffusioncoefficientofn-C12H16instationaryphaseis5.010-10m2/s.ThediffusioncoefficientofmobileisgreaterthanthestationaryphasebecauseitiseasierforthediffusionofsolutethroughHeliumgasthanthroughaviscousliquidphase.

Step by step solution

01

The deemter equation is taken in the form

H=Bx+Cx=(Cs+Cm)xCs=2k3k+12d2dsCm=1+6k11k224k+12r2DmB=2Dm

WhereDm=diffusioncoefficientofsoluteinmobilephasek=retentionfactord=thicknessofstationaryphaseDs=diffusioncoefficientofsoluteinstationaryphase

02

Diffusion coefficient of solute in mobile phase

H=6.010-5m2/sx+(2.0910-3s)xB=2DM=6.010-5m2/sDm=3.0105m2/sForthesecondterm,Cs+Cm=2.0910-3s=2k3(k+1)2d2Ds+1+6k+11k224(k+1)2r2dmconsumptionofcitrateandactivationofglycolysis.

03

Diffusion coefficient of solute in stationary phase

Substituting the values of all parameters to solve Ds

2.0910-3s=28.038.0+12(3.010-6m)2Ds+1+6(8.0)+11(80)224((8.0)+1)2(2.6510-4m)2(3.010-5m2/s)Ds=5.010-10m2/s

04

Diffusion coefficient in mobile phase

Diffusion coefficient in mobile phase=3.010-5m2/s5.010-10m2/s=6.0104

05

Reason why one of these diffusion coefficient is greater than the other

Diffusion coefficient in mobile phase is 6.010-4times higher than the diffusion coefficient in stationary phase. The diffusion coefficient of mobile is greater than the diffusion coefficient in the stationary phase because it is easier for the diffusion of solute through Helium gas than through liquid phase.

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Most popular questions from this chapter

The graph shows van Deemter curves for n-nonane at . in the 3.0-m-long microfabricated column in Box 24-2 with a -thick stationary phase.

van Deemter curves. [Data from G. Lambertus, A. Elstro, K. Sensenig, J. Potkay, M. Agah, S. Scheuening, K. Wise, F. Dorman, and R. Sacks, "Design, Fabrication, and Evaluation of Microfabricated Columns for Gas Chromatography," Anal. Chem. 2004, 76, 2629.]

(a) Why would air be chosen as the carrier gas? What is the danger of using

air as carrier gas?

(b) Measure the optimum velocity and plate height for air and for carrier

gases.

(c) How many plates are there in the 3 -m-long column for each carrier gas at

optimum flow rate?

(d) How long does unretained gas take to travel through the column at

optimum velocity for each carrier gas?

(e) If stationary phase is sufficiently thin with respect to column diameter, which of the two mass transfer terms (23-40 or 23-41) becomes negligible?

Why?

(f) Why is the loss of column efficiency at high flow rates less severe for

than for air carrier gas?

Retention time depends on temperature, T, according to the equation log t鈥r =(a/T) + b, where a and b are constants for a specific compound on a specific column. A compound is eluted from a gas chromatography column at an adjusted retention time t鈥r =15.0 min when the column temperature is 373K. At 363 K, t9r 5 20.0 min. Find the parameters a and b and predict t鈥r at 353K

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.

(a) What are the advantages and disadvantages of temperature programming in gas chromatography?

(b) What is the advantage of pressure programming?

(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?

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