# Research Activity: Separations and Analysis

Division: Chemical Sciences, Geosciences, and Biosciences

Primary Contact(s): Paul H. Maupin (<Paul.Maupin@science.doe.gov>;
301-903-4355)

Henry F. Shaw (<Henry.Shaw@science.doe.gov>; 301-903-3947)

Team Leader: William S. Millman

Division Director: William H. Kirchhoff

# Portfolio Description:

This activity addresses the scientific principles that underlie
energy-relevant chemical separations and analytical methods,
capitalizing on the synergistic relationship between these two areas of
chemistry.

The portfolio for separations science emphasizes, but is not limited to,
the separation of radionuclides and other metal ions, and seeks
molecular-level understanding to support advances in both large-scale
and analytical-scale separations. Molecular-level understanding is also
sought for separation methods that have the potential to significantly
impact energy use, such as membrane-based processes.

The analytical research portfolio emphasizes mass spectrometry and seeks
to elucidate the chemical and physical principles that underlie
ionization and excitation processes and modern approaches to mass
discrimination. A second major sector of the portfolio seeks to
understand and use the interaction of electromagnetic radiation with
matter in phenomena such as molecular fluorescence, laser ablation,
surface-enhanced Raman scattering, and magnetic resonance. Research to
understand chromatography at the molecular level reflects the synergy
between separations and analytical sciences. This activity also
contributes to the maintenance of the scientific infrastructure required
to meet as-yet-undefined challenges in separations and analysis.

# Unique Aspects:

This activity represents the Nation's most significant long-term
investment in solvent extraction, ion exchange, and mass spectrometry.
The supported research is characterized by a unique emphasis on
underlying chemical and physical principles, as opposed to the
development of methods and processes for specific applications.

# Relationship to Others:

The activity is closely coupled to the Department's stewardship
responsibility for actinide and fission product chemistry and to its
clean-up mission. It emphasizes the separation and analysis of actinide
and fission product elements and their decay products. The basic nature
of the research has led to advances in technologies ranging from those
that support nuclear non-proliferation efforts to the Human Genome
Project

# Significant Accomplishments:

This activity is responsible for such notable contributions as the
concept of host-guest complexation, for which Professor Donald Cram
(UCLA) shared the 1987 Nobel Prize in Chemistry; the use of the
inductively coupled plasma (ICP) for emission and mass spectrometry;
and, more recently, the concept of bifunctionality in ion-exchange
resins and solvent extraction. A Presidential Green Chemistry Award in
1997 was shared by researchers supported by this activity for their
contributions to the understanding of processes in supercritical carbon
dioxide that enabled the introduction of a chloro-fluorocarbon-free
process for the dry-cleaning industry. This new commercial process
relies on fundamental understanding developed with the support of this
activity.

# Mission Relevance:

The success of the Manhattan Project was, in large part, due to our
ability to develop industrial-scale processes for separating plutonium
from irradiated fuel. Thus began the intense interest of the Department
of Energy and its predecessor agencies in the science that underlies
separation processes. The missions of the Department have evolved, and
it must now face the legacy of accumulated wastes from the cold war era.
Knowledge of molecular-level processes is required to characterize and
treat these extremely complex mixtures and to understand and predict the
fate of associated contaminants in the environment. In addition,
separation science and technology have huge economic and energy impacts.
For example, distillation processes in the petroleum, chemical, and
natural gas industries annually consume the equivalent of 315 million
barrels of oil (\~5.4% of total petroleum consumption). It is further
estimated that separations processes account for more than 5% of total
national energy consumption. Separations are essential to nearly all
operations in the processing industries and are necessary for many
analytical procedures.

The Department and its predecessors were also driven to develop
analytical methodologies to support their early missions. Nuclear and
radiochemical analyses were supported and refined by developments in
analytical separations, such as solvent extraction and ion exchange. A
need for reliable potentiometric titration prompted the first use of
operational amplifiers in analytical chemistry and led to a revolution
in electrochemistry. Mass separation was required for assay in the form
of mass spectrometry and, in the form of the calutron, served as the
first method for the production of macroscopic quantities of separated
isotopes of uranium and other elements. As with separation science,
improved understanding of the underlying science is required to meet the
analytical challenges presented by the legacy of the cold war and the
future challenges of the Department as its missions and responsibilities
continue to evolve.

# Scientific Challenges:

Challenges in separation science include the development of a deeper
understanding of processes driven by small energy differences. These
include self-assembly and molecular recognition, crystallization,
dispersion, coalescence, and hysteresis in transport properties of
glassy polymer membranes. Improved understanding of solvation in
supercritical and other fluids is required, as is the development of
fundamental principles to guide ligand design. These, in turn, pose
challenges to analysts to generate the understanding required to
characterize amorphous materials through analysis of scattering data or
other methods. Other analytical challenges include single-molecule
detection and direct observation of bimolecular interactions and
reactions. A deeper understanding of laser-material interactions as well
as ionization and excitation sources for optical and mass spectrometric
analyses is also required. Significant challenges are posed by
elucidation of principles to underlie diagnostics at interfaces between
synthetic materials and biomolecules, at oxide-aqueous interfaces, and
to monitor spatial and temporal processes in, and on the surfaces of,
living cells. Though understanding at the molecular level is required,
there is currently insufficient knowledge to extend that understanding
from the molecular level to the nanoscale, to mesoscale, and finally, to
macroscale phenomena. Pursuit of that knowledge presents a major
challenge to this activity.

**Funding Summary:**

**Dollars in Thousands**

**[FY 2000]{.underline}** **[FY 2001]{.underline}** **[FY
2002]{.underline}**

**\$12,255 \$14,393 \$13,047**

> **[Performer]{.underline} [Funding Percentage]{.underline}**
>
> DOE Laboratories 53.0%
>
> Universities 47.0%

This activity provides funding for 47 university grants supporting about
57 students, 29 postdocs, and partially supporting about 44 faculty and
senior staff and 22 programs at national laboratories supporting
numerous senior staff, and additional students and postdocs. Programs at
the laboratories are typically multi-investigator efforts on problems
that require extensive participation by experienced scientists. These
programs act as the focal point for specific research efforts vital to
the DOE mission. This BES activity supports research at ORNL, ANL, and
PNNL, with smaller efforts at LBNL, BNL, and INEEL. Many of the research
efforts at the national laboratories involve collaborations with the
university and industrial communities.

**Projected Evolution:**

Separations research will continue to advance the understanding of
multifunction separations media; self-assembly for supramolecular
recognition (using designed, multi-molecule assemblies to attract
specific target species); synthesis of ionophores (molecules that
attract charged species); molecular-level understanding and control of
interface properties at the nanoscale; ligand design and synthesis of
extractant molecules; mechanisms of transport and fouling in polymer and
inorganic membranes; solvation in supercritical fluids; field-enhanced
mixing, and drop formation.

Analytical research will pursue characterization of interfacial
phenomena, with emphasis on chromatography; second-order phenomena in
NMR spectroscopy; elucidation of ionization and excitation mechanisms
for optical and mass spectrometry; single molecule detection and
characterization; nano- and micro-scale analytical methods; laser-based
methods for high-resolution spectroscopy and for presentation of samples
for mass spectrometry. Enhanced Raman spectroscopy will be investigated
and exploited. The use of quadrupole ion traps to study gas-phase ion
chemistry will continue.

An expanded activity would support work to understand the self-assembly
process by investigating energetics and rate-controlling steps;
increased effort in characterization of the aqueous-oxide interface, as
well as general liquid-solid and liquid-liquid interfaces; analysis of
scattering and NMR data to characterize amorphous media; extension of
solid-state NMR to more elements in the periodic table; enhanced effort
in molecular modeling to support ligand design; improved analysis of
near-edge x-ray absorption to directly probe electronic states
ultimately responsible for chemical reactions; field-enhanced
spectroscopy; expand university effort in manpower-intensive organic and
inorganic synthesis; provide support to enhance collaboration between
universities and national laboratories; and maintenance and upgrade of
national laboratory infrastructure. The activity will evolve to meet the
challenges in self-assembly, characterization of interfaces,
single-molecule detection, and gas-phase ion chemistry. A synthesis of
results of analytical research to enable collection of basic data,
ligand design to control possible reactions, as well as modeling and
computational science, will be required to enable the prediction of
macroscopic behavior from known molecular properties.

04 February 2002