Regions of the electromagnetic spectrum

Representation of an electromagnetic wave

[Co(en) 3 ] 3+ complex ion

Pb2+ EDTA complex

Pentaammine isothiocyanatocobalt(III) ion

Zeolite-Y

Zeolite-A

Pokok Bahasan
1. Review Infrared Spectroscopy 2. Infrared Spectroscopy of Inorganic Molekul 3. Infrared Spectroscopy of Zeolite Identification of dealumination process Identification of isomorphous reaction process 1. Infrared Spectroscopy of Clay Identification of pillarization process 1. Infrared Adsorbed Molecule on zeolite structure and metal oxide 6. Conclusion

Regions of the electromagnetic spectrum

Representation of an electromagnetic wave

Change in the dipole moment of a heteronuclear diatomic molecule A molecule that has infrared absorptions it must possess a specific feature, i.e an electric dipole moment of the molecule must change during the vibrations

Normal modes of vibration of linear and bent XY2 molecules

+ and denote vibrations moving upwards and downwards, respectively, in direction perpendicular to the palne of the paper

Normal modes vibration in H 2 O Normal modes vibration in CO 2

1 is Raman-active 2 and 3 are Infrared-active

Frequency vibrations of Various Inorganic Molecules (1/cm)

Infrared spectra of (a) dihydrate, (b) hemihydrate, and (c) anhydrous CaSO4

Spektra inframerah molekul NiF 2

Jenis isotop unsur-unsur logam menentukan frekwensi vibrasi inframerah

Vibrational Frequencies of XY2 Type Metal Halides

Compound
BeF 2 BeCl 2 BeBr 2 BeI 2 MgF 2 MgCl 2 MgBr 2 MgI 2

Structure
linear linear linear linear linear linear linear linear

1 (cm -1 )
(680) (390) (230) (160) 550 327 198 148

2 (cm -1 )
345 250 220 (175) 249 93 82 56

3 (cm -1 )
1555 1135 1010 873 842 601 497 445

(680) frequencies Raman-active or Infrared-inactive

Normal modes of vibration of planar (a) and pyramidal (b)

Frequency vibrations of Various Molecules of planar and pyramidal of XY3 (1/cm)

Daerah near infra red

Raman Spectra of the SnX 3 - ions in diethyl ether extracts from SnX in HX solution

Normal modes of vibration of tetrahedral (a) and square planar (b) of XY4 molecules

Frequency vibrations of Various Molecules of tetrahedral and square planar of XY4 (1/cm)

Vibrational Modes of NH 4 Cl

5 and 6 are lattice vibrational modes

Cl KClO3

I KIO3

KClO3 Infrared spectra of KClO 3 (solid line) and KIO 3 (dash line)

PBU

SBU

Primary and Secondary Building Unit Zeolites Structure

1) Garis tebal : Tetrahedral internal (tidak sensitif struktur, sensitif komposisi kimia, rasiio Si/Al)

2) Garis putus-putus : Jalinan Eksternal (sensitif struktur, tidak sensitif komposisi kimia)

Assignment infra merah Zeolite Tetrahedral Internal

Jenis vibrasi
Regangan asimetris Regangan simetris Bend T-O

Jalinan Eksternal
Jenis vibrasi (cm -1 )
750-820 1050-1150 650-500 300-420

(cm -1 )

1250-950 Regangan asimetris 720-650 420-500 Regangan simetris Cincin ganda Pori terbuka

IR spectra of OH groups in Mazzites Zeolite of Si/Al = 4,4 ; 10 ; 30

(a)activated mazzite, (b) ammonia adsorption, (c) pyridine adsorption, (d) reacting with pyridine (a minus c)

IR spectra of OH groups MAZ 4,4 (a), (b) after benzene adsorption, (c) a-b

IR spectra of OH groups MAZ 4,4 (a), 10 (b), 30 (c) after benzene adsorption

1) Garis tebal : Tetrahedral internal (tidak sensitif struktur, sensitif komposisi kimia, rasiio Si/Al)

2) Garis putus-putus : Jalinan Eksternal (sensitif struktur, tidak sensitif komposisi kimia)

H-Zeolite-Y H-Zeolite-ZSM20

Dealuminated Zeolite-US Dealuminated Zeolite-Y Dealuminated Zeolite-ZSM20

IR Spectra in the region lattice vibrations of hydrated Faujasite type Zeolites

Dealumination process

Infrared spectra padatan hasil reaksi isomorphous abu layang dan (NH4)2HPO4

Diambil dari IR Spectroscopy in catalysis, Catalysis today 68 (2001) 263-281 EBOOK-IR Review, halaman 312

Unit cell of faujasite-type (X and Y) zeolites, including cation sites. In faujasite zeolites, the cations in the beta-cages and the double six-ring (SD6R, the hexagonal prism) (i.e., at sites SI, SI, and SII) are sterically inaccessible to nitrogen, and so only the supercage cations (i.e., those at SII and Diambil dari Adsorbent Fundamental and Application, EBook, Chapter X, hal 287

(Top) Site II cation on six-membered oxygen ring as the basic unit on A and X zeolites. T denotes Si or Al. (Bottom) Geometry-optimized cluster model to represent the chemistry of Ag-zeolite.

Diambil dari Adsorbent Fundamental and Application, EBook, Chapter VII, hal 174

(a) Extra-framework cation sites in X- and Y-type zeolites. (b) Far- infrared spectrum of Na-Y with band assignments to cation sites according to [232]. (c) Experimental IR spectrum in comparison to simulated spectra calculated according to the shell model and occupancy of different cation sites. (d) Experimental spectrum in comparison to power spectra simulated by MD at occupancy of different cation sites (parts c and d from [79] with permission) halaman 67

Far-infrared (FIR) spectra of alkali-metal cation-exchanged faujasites and H-Y zeolite

IR Spektra Montmorillonit yg di treatment dgn asam 6 M HCl pada variasi Waktu (a) 0, (b) 2, (c) 4, (d) 6, (e) 8, (f) 10, (g) 12, (h) 18, (i) 24 dan (j) 30 jam

 Pita yg paling intensif didekat 1048 cm-1 diindikasikan sbg vibrasi stretching Si-O dari lapisan tetrahedral. Pita 524 cm-1 adalah vibrasi Si-O-Al ( dimana Al adalah kation oktahedral) Pita 466 cm-1 adalah vibrasi bending Si-O-Si. Pita serapan pada 621 cm-1 ini sesuai dgn vibrasi tegak lurus dari kation oktahedral (M-O-Si) dimana M adalah Al, Mg dan Li Tiga puncak pada daerah bending OH adalah : (a) 917 cm-1 (Al2OH) (b) 886 cm-1 (AlFeOH) (c) 850 cm-1 (AlMgOH) Al oktahedral disubstitusi oleh Fe dan Mg. Intenditas yg rendah dari puncak pita MgAlOH mengindikasikan kandungan Mg yang rendah. Puncak doublet pada 799 dan 779 mengindikasikan adanya campuran mineral lain dalam hal ini adalah mineral kuarsa.

 Pita 524 cm-1 adalah vibrasi Si-O-Al ( Al adalah kation oktahedral) Intensitas puncak 524 berkurang dgn kenaikan waktu Pita doublet 799 dan 779 indikasi adanya mineral kuarsa, Intensitas puncak 799 bertambah dgn kenaikan waktu (dealuminasi kuarsa) Tiga puncak pada daerah bending OH adalah : (a) 917 cm-1 (Al2OH) (b) 886 cm-1 (AlFeOH) (c) 850 cm-1 (AlMgOH) Ketiga puncak berkurang dgn kenaikan waktu (dealuminasi, penukaran kation) Pita 1048 cm-1 diindikasikan sbg vibrasi stretching Si-O (tetrahedral) Puncak makin membesar indikasi terbentuknya amorphous silika

IR Spektra Hectorite yg di treatment dgn asam 0,25 M HCl pada variasi Waktu (a) 1, (b) 3, (c) 5 dan (d) 8 jam

Hectorite adalah trioktahedral smectite yg berisi Mg dan Li sebagai kation oktahedral Puncak 654 cm-1 bending OH

Puncak 1012 cm-1 stretching Si-O Puncak 701 cm-1 bending Si-O tegak lurus bidang Puncak 467 cm-1 bending Si-O dlm bidang Pita 524 cm-1 adalah vibrasi Si-O-Al ( Al adalah kation oktahedral) Intensitas puncak 524 berkurang dgn kenaikan waktu Tiga puncak pada daerah bending OH adalah : (a) 917 cm-1 (Al2OH) (b) 886 cm-1 (AlFeOH) (c) 850 cm-1 (AlMgOH) Ketiga puncak berkurang dgn kenaikan waktu (dealuminasi, penukaran kation) Pita 1048 cm-1 diindikasikan sbg vibrasi stretching Si-O (tetrahedral) Puncak makin membesar indikasi terbentuknya amorphous silika

IR Spektra Smectite yg di treatment dgn asam 6 M HCl pada variasi suhu (a) asli, (b) 60oC dan (c) 95oC

IR Spektra Hectorite yg di treatment dgn asam HCl pada variasi konsentras (a) 0, (b) 0,1, (c) 0,25 dan (d) 0,5 M

Natural Bentonite
Surfactan ~ 3 % b/b Acid Leaching Hydrotermal Calcination

HEKSAGONAL MESOPORE CLAY (HMC)

Infrared Spectra Natural Bentonite and Leached bentonite resulted from nonswelling leaching in various concentrasion of Hydrochloride Acid, (a) Natural Bentonit (b) 7M (c) 8 M,(d) 9 M and (e) 10 M

Difractogram Spectra Natural Bentonite and Leached bentonite resulted from nonswelling leaching in various concentrasion of Hydrochloride Acid, (a) Natural Bentonit (b) 7M (c) 8 M,(d) 9 M and (e) 10 M

Infrared Spectra Natural Bentonite and Leached bentonite resulted from swelling leaching in various concentrasion of Hydrochloride Acid, (a) Natural Bentonit (b) 4M (c) 5 M, and (d) 6M

Difractogram Spectra Natural Bentonite and Leached bentonite resulted from swelling leaching in various concentrasion of Hydrochloride Acid, (a) Natural Bentonit (b) 4M (c) 5 M, and (d) 6M

Difractogram Spectra of Composed Bentonite prepared from Leached bentonite resulted by swelling method in various concentrasion of Hydrochloride Acid and C14TMA (a) 4M (b) 5M and (c) 6M

Spectra Infrared of Heksagonal Mesopore Clay a) before calcination b) after calcination

d001 2,10o, 42,03

Difraktogram Spectra of Heksagonal Mesopore Clay (a) before calsination (b) after calcinations

d001 2,14o, 41,13

d110 3,88 , 22,73

o

d200 4,42o, 19,94 d110 3,93o, 21,83 d200 4,46o, 19,04

Two dimension Ilustration of HMC d = basal spacing ~ 41,31 pore

a = distance between center pore t = pore wall thickness, for MCM-41
~ 6-12
a d

a=

d 41,13 A = 47,49 A = 1 cos 30 3 2

Pore diameter = a t = 47,49 12 = 35,49

t = 6-12 A

Isoterm Adsorption-Desorption
Iso term Ad so rp si-d eso rp si H M C
350 300 250 V (cc/g) 200 150 100 50 0
0 0 .2 0 .4 0 .6 0 .8 1

SBET = 614,647 m2/g dpore = 36,49

a dsorpsi d esorpsi

P/Po

Pore Size Distribution

0.25 0.2 Vp/delta rP 0.15 0.1 0.05 0 -0.05 0 5 10 15 20 rP rata-rata 25 30 35 40 13,2

The FTIR spectrum of Clinoptilolite The XRD patterns of Cp sample (Fig. 1) showed that the main crystalline phases correspond to clinoptilolite. The FTIR spectrum of Cp is shown in Fig. 2. The peaks at 3600, 3440 cm-1 are related to stretching mode of H-O-H, the peaks at 1080 and 1150 cm-1 belong to antisymmetrical stretching and peaks at 680 and 740 cm-1 are symmetricall stretchings of SiO4 and AlO4, respectively

(Top) Site II cation on six-membered oxygen ring as the basic unit on A and X zeolites. T denotes Si or Al. (Bottom) Geometry-optimized cluster model to represent the chemistry of Ag-zeolite.

Diambil dari Adsorbent Fundamental and Application, EBook, Chapter VII, hal 174

Diambil dari IR Spectroscopy in catalysis, Catalysis today 68 (2001) 263-281 EBOOK-IR Review, halaman 312

Zeolite framework vibrations according to the interpretation of Flanigen et al. (adopted from[112]); 1, solid lines: intra-tetrahedral vibrations; 2, broken lines: inter-tetrahedral vibrations Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 51

Wavenumbers of various framework vibrations as a function of the mole fraction of aluminum in tetrahedral (T) sites of the zeolite framework; s indicates the slope, i.e., the decrease of the wavenumber (cm1) per 0.1 atom fraction of Al ion substitution (adopted from [112]). D6R means double six-membered ring, ns and nas stand for symmetric and asymmetric stretching modes, respectively (cf. text and list of abbreviations) Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 52

Approximate assignments of observed lattice vibrational frequencies of Na-X zeolite [246] based on calculations [113]

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 53

Raman spectra of zeolites (a) Na-Y (nSi/nAl = 2.6) and (b) Na-X (nSi/nAl = 1.18)

Raman spectra of ion-exchanged Y-type zeolites (nSi/nAl = 2.6), viz. (a) Na-Y, (b) KY, (c) Rb-Y, (d) Cs-Y Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 59

Far-infrared (FIR) spectra of alkali-metal cation-exchanged faujasites and H-Y zeolite

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 65

(a) Extra-framework cation sites in X- and Y-type zeolites. (b) Far- infrared spectrum of Na-Y with band assignments to cation sites according to [232]. (c) Experimental IR spectrum in comparison to simulated spectra calculated according to the shell model and occupancy of different cation sites. (d) Experimental spectrum in comparison to power spectra simulated by MD at occupancy of different cation sites (parts c and d from [79] with permission) halaman 67

Calculated and experimental FIR spectrum of Ba-ZSM-5 (nSi/nAl = 13), adopted from [363] with permission

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 69

Comparison of far-infrared spectra of zeolites Na-Y and K-Y before and after adsorption of pyrrole [371] and pyrrolidine (from [372] with permission) Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 73

Infrared spectra in the OH stretching region of Y-type zeolite after dealumination via steam treatment. C alcined in A: moist air at 813 K; B: self-steam at 813 K; C: moist air at 1033 K; D: self-steam at 1033 K [411]

Wavenumbers and intensities of the OH stretching bands of a homologous series of zeolites, viz. mordenites ion-exchanged with alkaline earth cations [443 ]

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 79 dan 83

Correlation between the absorbance of the OH stretching band produced on sorption of H2S into faujasite-type zeolites and the population of the SIII sites (cf. Fig. 16a) by Na+ cations [454] Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 85

Gmelinite cage, hexagonal prism and cancrinite cage of the offretite structure and indication of crystallographically different oxygen atoms and corresponding OH groups therein [487]

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 89

Infrared bands of OH groups in hydrogen offretite (a: with 2.3 K+ cations per unit cell left after exchange; b: with 0.6 K+ cations per unit cell left after exchange): Left: before (full line) and after (dotted line) adsorption of pyridine. Right: before (full line) and after (dotted line) adsorption of ammonia [487]

Diffuse reflectance IR spectra of H-ZSM-5 (adopted from [546])

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 98

Near-infrared spectra of H-ZSM-5 with combination bands, n(OH)+d(OH) on increasing activation temperatures (adopted from [557])

Calculated power spectra of zeolites H-Y and D-Y in the mid-infrared framework region in comparison with the experimental INS spectrum of H-Y (from [577])

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 100 dan 104

INS spectra of bulk pyrrole obtained with the spectrometers (a) TFXA and (b) IN1BeF and of pyrrole adsorbed in (c) Na-Y and (d) Rb-Y; the asterisks indicate the most intense peaks, cf. text (from [585])

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 105

Infrared fundamentals of molecular deuterium, nitrogen and oxygen adsorbed on A-type zeolites [587]

Supercage of zeolite A with the main cation positions and symmetry axes [588]

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 107 dan 108

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 113

IR spectra of CO adsorbed at 0.13 mbar on autoreduced Ru, Na-Y in the temperature range 75298 K [624]

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 113

Schematic representation of the fundamental vibrations of nitrous oxide,N2O

Schematic representation of the fundamental vibrations of carbon dioxide, CO2; the mode n 2 is twofold degenerated ( n 2a, n 2b)

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 119 dan 121

Top : Sorption geometries of (a) CO2 and (b) N2O in zeolite Na4Ca4-A. Bottom :Observed fundamental vibrations n 3 (a) of CO2 and n 3(b) and n 1 (c) of N2O in zeolite Na4Ca4-A (adopted from [596])

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 120

Infrared spectra of methane,CH4, adsorbed on NaA; the spectra obtained at 104 and 105 mbar (adopted from [599])

Schematic representation of the fundamental vibrations of the bent triatomic molecules of sulfur dioxide, SO2, hydrogen sulfide,H2S, and water, H2O

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 123 dan 124

Infrared spectra of water vapor adsorbed on H-ZSM-5 at low pressures (1051 mbar); the spectra obtained at 104 and 105 mbar were expanded by the factors 5 and 10, respectively (adopted from [127])

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 113

Calculated potential energy surface for the adsorption of a single water molecule on a zeolitic Brnsted site (bridging OH group); AD: adsorption energy,PT: proton transfer energy (in kJ mol1), showing the hydroxonium ion as a transition structure and not in an energy minimum [655, 656]

Hydroxonium ion on a zeolite surface stabilized by a second water molecule where both surface species, (H2O)2 and (H3O+ H2O) become stable [655, 656]. For the meaning of AD and PT see caption of Fig. 43 or list of abbreviations

Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 128 dan 129

Scheme for the quantitative evaluation of zeolite spectra using integrated or maximum absorbance [128] Diambil dari Molecular Sieves, Sciences and Technology, Characterization I, Vibrational Spectroscopy, EBOOK halaman 36