BEL-CAT Application note

CAT-APP-001

Temperature Programmed Desorption measurement <Measurement of energy of desorption and adsorption heat>
6 June 2003 Kazuyuki Nakai Kaori Nakamura In acid type zeolite, acidic site on the surface influences the catalytic action significantly. It is essential to determine the strength and the amount of the acidic point for the evaluation of acid type zeolite. Calorimeter and ammonia TPD are used as the methods to determine the property. However, calorimetric measurement requires skill and sample pretreatment may not sometimes be suitable for some catalysts. Acid strength and acid quantity can now be evaluated easily with automatic temperature programmed desorption instruments that have been placed on the market in recent year.

[Introduction]
TPD(Temperature Programmed Desorption) was first proposed in 1963 by Amenomiya and Cvetanovic 1). When increasing thermal energy exceeds adsorption energy of molecules previously adsorbed during pretreatment these molecules desorb from the surface. These desorbed molecules are brought to a detector by carrier gas and quantified by the detector. Thermal Conductivity Detector (TCD), Mass Spectrometer and etc. is used as the detector. Amenomia et al. suggested the following relation between heating rate and active gas molecules assuimng there is homogeneous adsorption on the surface and no readsorption or diffusion 2:

TP2 Ed E d A0 log = 2.303RT + log RC P

Tp

()

Ed A0 C

desorption peak temperature (K) heating rate (K/min.) energy of desorption (kJ/mol) quantity adsorbed constant (related to desorption rate)

Change in heating rate shifts the desorption peak temperature. Plotting log(Tp2/) to 1/Tp, linear line can be obtained and energy of desorption(Ed) can be calculated from the slope. In case readsorption occurs freely, adsorption heatH can be calculated in same plot 2). Murakami and Niwa et al. deemed the above equation of Amenomia et al. insufficient and proposed the following 3):

(1 )2 (H RTP )2 A0W H ln(TP ) ln + ln = P 0 exp(S / R ) F RTP

W F P0
Sample weight () Actual flow rate (ml/min.) Coverage at peak temperature Atmospheric pressure

()

The above equation indicates that the peak temperature is influenced by acid amount as well as contact time. W/F change results in peak temperature change. Plotting ln(Tp)-ln(A0W/F) to /Tp, linear line can be obtained and heat of adsorption(H) can be calculated from the slope.

BEL-CAT Application note

CAT-APP-001

[Experiment]

In TPD measurement, energy of desorption (Ed) of JRC-Z5-25H with changing heating rate is calculated using equation of Amenomiya. Instrument S/N Sample Sample weight Carrier gas flow volume Pretreatment program Gas 0:He 0:He 0:He 0:He 4:NH3 0:He in 50 60 40 10 30 5 Target temperature 500 500 100 100 100 100 BEL-CAT CAT-4 JRC-Z5-25H 0.04949 g (Same sample is used in every measurement) 30sccm

Measurement program Waiting time for TCD stabilization Target temperature Heating rate Dwell time

20 min 500 C 2, 5, 10, 15 C/min 30 min

BEL-CAT Application note

CAT-APP-001

[Result]
JRC-Z5-25H 14000 13000 12000
TCD [V]

1.86/min 4.83/min 9.62/min 14.6/min

11000 10000 9000 8000 95 145 195 245 295 345 T [] 395 445 495 545

Fig. 1: TPD spectrum Heating rate/Kmin1 1.86 4.83 9.62 14.56 Sample weight/g Tp/K log(TP2/) 0.0495 650 5.36 0.0495 671 4.97 0.0495 685 4.69 0.0495 695 4.52 Table 1: Numeric data 1/TP 0.00154 0.00149 0.00146 0.00144 log(W/F)+3 0.159 0.173 0.182 0.188

5.6 5.4 5.2

(Tp 2 /)

y = 8.45E+03x - 7.63E+00 R2 = 9.99E-01

5.0 4.8 4.6 4.4 4.2 4.0 0.00142

0.00144

0.00146

0.00148 1/Tp

0.00150

0.00152

0.00154

0.00156

Fig. 2: Amenomiya equation

BEL-CAT Application note

CAT-APP-001

[Calculation of energy of desorption]

Ed = 8.45E+03 2.303 R R=8.31 J/mol

Energy of desorption (Ed) = 162 kJ/mol

1) 2) 3) 4) 5)

Reference:

Amenomiya, Y. and Cvetanovic, R.J., J. Phys. Chem., 67, 144 (1963). Cvetanovic, R.J. and Amenomiya, Y., Advan. Catal., 17, 103 (1967). Sawa, M., Niwa, M. and Murakami, Y., Zeolites. 10, 307 (1990). Iwamoto, M. Characterization of Solid catalyst, catalysis course 3, 152, Kodansha (1985). Niwa, Catalysis, 33, 249 (1991).