Research Infrastructure at the

Department of Chemistry

Neil Brooks
 Outline

• Overview, basics and examples of core infrastructure

– Total X-ray Fluoresence Spectroscopy – TXRF
– IR/Raman spectroscopy
– Differential Scanning Calorimetry (DSC)
– Nuclear Magnetic Resonance (NMR)
– Single Crystal X-ray Crystallography (SC-XRD)
• Summary
• Assorted other equipment
TXRF – Total X-ray Fluoresence Spectroscopy
 TXRF: key parameters

• Two Bruker S2 Picofox TXRF spectrometers in the group

• Key information: accurate elemental compositions/ratios
• Fast and easy
• Low detection limit possible (e.g. ppb)
• Multi-element sample analysis
• Difficult to detect elements lighter than chlorine
– Ejected X-rays from lighter elements low in energy (matrix effects)
TXRF: technique
TXRF: technique
 TXRF example: [Br] and [Cl] in ionic liquids
Measured Br conc. in [C4mim][Tf2N] (ppm)

12000 [Br] in Recovery RSD

10000
[C4mim][Tf2N] (ppm) rates (%) (%)
8000
10000 105 6
6000
4000 105 9
4000

2000 2000 113 4

0 1000 100 6
0 2000 4000 6000 8000 10000
Expected Br conc. in [C4mim][Tf2N] (ppm) 100 100 6
Measured Cl conc. in [C4mim][OAc] (ppm)

[Cl] in Recovery RSD

10000
[C4mim][OAc] (ppm) rates (%) (%)
8000
10000 92 7
6000
4000 90 8
4000 2000 94 14
2000 1000 97 5
400 91 10
0
200 96 10
0 2000 4000 6000 8000 10000
Expected Cl conc. in [C4mim][OAc] (ppm) 100 98 13
IR/Raman Spectroscopy
 IR: technique

• FT-IR spectrometer Bruker Vertex 70 with Raman module Bruker

RAM II

• Vibrational spectroscopy
– Key information: identification of particular bond vibrations
 IR: technique

• FT-IR spectrometer Bruker Vertex 70 with Raman module Bruker

RAM II

• Vibrational spectroscopy
– Key information: identification of particular bond vibrations
• Spectral range 4500 to 400 cm-1
– Transmittance mode (sample prep necessary)
– Attenuated total reflection
• Diamond or ZnSe crystal
• Fast (ca. 1-2 minutes)
• Far infrared (400 to 40 cm-1) also possible
• Variable resolution (e.g. 1, 2, 4 cm-1)
• Required sample: <5 mg
 Raman: technique

• FT-IR spectrometer Bruker Vertex 70 with Raman module Bruker

RAM II

• Different selection rules to IR

• Nd-YAG laser λ = 1064 nm
– Variable laser power (1-500 mW)
– Fluoresence can be problem
• Spectral range 3600 to 40 cm-1
• Variable resolution (e.g. 1, 2, 4 cm-1)
• Sample dependent collection time (typically 2 minutes – 2 hours)
– No background collection
• Liq. N2 cooled Ge CCD detector
• Required sample: 50-500 mg
• Surface Enhancement possible (SERS)
 Raman example: adsorption of 1H-benzotriazole
on silver substrate in [Ag(MeCN)4]2[Ag(Tf2N)3]

• text

Pure Ag-LMS 1H-benzotriazole (0.1 M)

0.1M benzotriazole in Ag-LMS on Ag surface

0.1M benzotriazole in Ag-LMS (bulk)

Pure benzotriazole

Pure Ag-LMS
DSC – Differential Scanning Calorimetry
 DSC: technique

• Mettler-Toledo DSC822e module

• Key information: phase transition temperatures/energetics
• Required sample: 2-5 mg
• Temperature range -60 to 250 °C
• Variable heating rate (typically 10 °C/min)

• Complimented with polarised optical microscopy (thermomicroscopy)

on an Olympus BX-60 polarising microscope equipped with a Linkam
THMS 600 hot stage. Temperature range: -196°C - 600°C.
 DSC example: eutectic behaviour of
DMSO2/acetamide mixtures

DSC traces of DMSO2/acetamide mixtures Tamman plot

NMR – Nuclear Magnetic Resonance Spectroscopy
 NMR: technique

• Energy states of spin active nuclei split from degeneracy inside a

magnetic field
– E/M radation applied to populate the higher energy state
– Difference in energy of higher and lower states measured is a
function of the nucleus and its environment
• Key information: chemical information about nucleus environment
• 300, 400 and 600 MHz spectrometers available
• Nucleus must be NMR active
– Most common nuclei: 1H, 13C, 31P, 19F
– Can not have unpaired electrons
– Must have sufficient natural abundance
• Liquid state: sample must be a liquid or disolved in a solvent
• Required sample: 5-20 mg
Single Crystal X-ray Crystallography (SC-XRD)
 SC-XRD: technique

• Key information: absolute three-dimensional crystal structure

– Allows the resolution of atom positions up to ±0.001 Å
– Accurate bond and intermolecular distances
• Scattering (diffraction) of X-rays from ordered array of molecules in a
crystal leads to diffraction pattern (Bragg’s law: nλ=2dsinθ)
• Diffraction pattern is directly related to the three-dimensional electron
density pattern
– Phase problem
– Imperfect crystals
 SC-XRD: practicalities

• Must have (good quality) single crystal!

• Crystal size (each dimension) must be 0.05 to 0.5 mm
– Larger crystals can be cut to size
– Smaller crystals may be possible but will take longer
• Crystal growth
– Evaporation of saturated solution
– Addition of antisolvent
– Growth from melt by slow cooling
• What can be determined?
– Can be used for phase identification
• Crystal structure already known (unit cell check)
– New structure determination
– Elemental composition (on specific lattice sites)
 SC-XRD example: structure of Ag-LMS

• First synthesised a Cu-LMS of formula [Cu(MeCN)4][Tf2N]

– Melting point 65 °C
• New Ag-LMS of formula [Ag(MeCN)~2][Tf2N]
– Melting point 18 °C
• Slow cooling of Ag-LMS gave good quality crystals
• Structure determined as [Ag(MeCN)4]2[Ag(Tf2N)3]
 SC-XRD: case study structure of Ag-LMS

• If [Ag(MeCN)4]2[Ag(Tf2N)3] is heated at 50 °C for a period of time new

crystals appear

• Crystal structure analysis shows the new compound is [Ag(MeCN)Tf2N]

– One-dimensional polymeric structure
– Melting point 90 °C
 Overview

Sample prep Amount Experiment Analysis Difficulty

required sample time time
TXRF Yes ppm <1 hour 1 hour Easy
IR No <5 mg 2-5 minutes 15 minutes Easy
Raman No 50-500mg 0.5-4 hours 1 hour Medium
DSC No 2-5 mg Several hours 15 minutes Easy
NMR Yes 5-20 mg 0.5-4 hours 1 hour Medium
SC-XRD Yes one crystal 1 day 1+ week Hard
 Assorted other equipment

• Mass spectrometry
• Absorption spectroscopy (UV-VIS-IR)
– Varian Cary 5000: UV-VIS-NIR spectrophotometer (175-3300 nm)
• Luminescence spectrometers
• Viscosimetry
– Brookfield cone plate viscosimeter (LVDV-II+ Programmable
Viscometer) with cone spindle CPE-40
• X-ray powder diffraction setup with rotating Mo-anode
– SAXS and WAXS
• CHN microanalysis
– CE Instruments EA-1110 CHN elemental analyser
 Practicalities

• Contact me by email: neil.brooks@chem.kuleuven.be to notify interest

– Set up meeting to discuss how to proceed

Acknowledgements
• Tom Vander Hoogerstraete (Chemistry)
• M. Ganapathi (MTM)