Spectrochimica Acta Part B 110 (2015) 31–44

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Spectrochimica Acta Part B

journal homepage: www.elsevier.com/locate/sab

Review

Kinetic energy discrimination in collision/reaction cell ICP-MS:

Theoretical review of principles and limitations
Noriyuki Yamada
Agilent Technologies International Japan, Tokyo, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Kinetic energy discrimination (KED) is one of the means to control cell-formed interferences in collision/reaction
Received 17 March 2015 cell ICP-MS, and also a technique to reduce polyatomic ion interferences derived from the plasma or vacuum
Accepted 18 May 2015 interface in collision cell ICP-MS. The operation of KED is accurately described to explain how spectral interfer-
Available online 30 May 2015
ences from polyatomic ions are reduced by this technique. The cell is operated under non-thermal conditions
Edited by A Bogaerts
to implement KED, where the hard sphere collision model is aptly employed to portray the transmission of
ions colliding with the cell gas that they don't chemically react with. It is theoretically explained that the analyte
Keywords: atomic ions surmount the energy barrier placed downstream of the cell and the interfering polyatomic ions do
Inductively coupled plasma mass spectrometry not due to their lower kinetic energy than the atomic ions, resulting in polyatomic interference reduction. The
ICP-MS intrinsic limitations of this technique are shown to lie in the statistical nature of collision processes, which causes
Collision reaction cell the broadening of ion kinetic energy distribution that hinders efficient KED. The reaction cell operation with KED,
Kinetic energy discrimination where plasma-derived interferences are reduced by the reactive cell gas while cell-formed interferences are sup-
KED pressed by the energy barrier, is also described in a quantitative manner. This review paper provides an in-depth
understanding of KED in cell-based ICP-MS for analysts to make better use of it.
© 2015 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2. Collision processes in the cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.1. Decrease of ion kinetic energy by collision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.2. Initial ion kinetic energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.2. Number of collisions in the cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.3. Kinetic energy and scattering angle after a collision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.4. Ion kinetic energy after multiple collisions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2.5. Ion trajectories in non-thermal cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3. KED in collision cell ICP-MS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.1. Potential barrier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.2. Efficiency of KED . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3.3. Energy spread caused by multiple collisions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.4. Ion signal dependence on collision gas density (gas flow rate) of different collision gases . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.5. KED against doubly charged ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4. KED in reaction cell ICP-MS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.1. Non-thermal reaction cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.2. Reactant ion intensity in the cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
4.3. Kinetic energy of reactant ions in the cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4.4. Ar+ and Ca+ signals in H2 reaction cell ICP-MS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44

http://dx.doi.org/10.1016/j.sab.2015.05.008
0584-8547/© 2015 Elsevier B.V. All rights reserved.
32 N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44
1. Introduction
Around the turn of the century collision/reaction cell ICP-MS was
commercially developed to address the problem of spectral interfer-
ences, which had been one of the major limitations in ICP-MS. Since
then, it has rapidly grown popular in analytical laboratories around
the world as a versatile technique to mitigate or circumvent interfering
ions. Among the different types of cells that have been developed to
reduce the spectral interferences derived from the plasma or the
sampling interface, there is a common issue peculiar to this technique —
the formation of undesirable ions within the cell through ion-molecule
reactions. These ions can be produced not only through the reactions
with the cell gas (in reaction cells) but also those with residual impurity
gases such as water and hydrocarbons (in both collision and reaction
cells). If the product ions have the same m/z as the analyte ions of
interest and no measure is taken to suppress them, they will interfere
with the analyte ion, thereby ruining the reduction of the original
interferences that is to be achieved by the intended collision or reaction
processes in the cell.
The collision/reaction cells are effectual only when the interferences
from the plasma or interface and those from cell-formed product ions
are suppressed at the same time. While adding gas to the cell to reduce
the former, three different approaches have been used to suppress the
latter, that is, the signals of the detrimental product ions. 1) The dynam-
ic reaction cell [1] prevents the formation of undesirable reaction
products by using a band-passing quadrupole as an ion guide in the
cell, which quickly ejects unnecessary (low-mass) ions before they
produce undesirable ions through reactions with gas molecules.
2) The most recently developed ICP-QQQ [2] removes the unnecessary
ions prior to the cell using an additional quadrupole mass filter, which
allows only the analyte ions of interest (and the isobaric interfering
ions) into the cell, and hence restricts the unnecessary reactions that
would otherwise occur and yield undesirable ions in the cell. 3) KED
[3] serves to prevent the transmission of the product ions toward the
detector, while allowing their formation in the cell. Since the product
ions that have exited the cell have lower kinetic energy than the atomic
analyte ions under non-thermal conditions, they are selectively blocked
by the potential barrier of appropriate height after the cell. The barrier
can simply be established by setting the DC bias voltage of the quadru-
pole mass filter after the cell to slightly more positive voltage than that
of the ion guide in the cell. KED has been used in both collision cells and
reaction cells under non-thermal conditions. In this paper, the cell is
referred to as collision cell when the cell gas is unreactive with the
analyte and interfering ions, and as reaction cell when the cell gas is
reactive with the analyte or interfering ions. The same cell can be a
collision cell or reaction cell depending on the cell gas used and the
ions considered.
Besides the reduction of cell-formed product ion interferences, KED
also plays an essential role in collision cell ICP-MS to reduce polyatomic
ion interferences that are derived from the plasma or interface. Under
typical operating conditions, an ion undergoes multiple collisions with
gas molecules (or atoms) while it travels through the multipole
ion guide extending from the entrance to the exit of the cell. It exits
the cell with reduced kinetic energy as a result of these collisions.
Atomic ions (analyte ions) lose less kinetic energy than the isobaric
polyatomic ions (interfering ions), thus an energy difference is pro-
duced between the two ion species of the same mass. By a potential
energy barrier of appropriate height placed after the cell, the slower
polyatomic ions are blocked while the faster atomic ions overcome
the barrier and reach the detector. Thus polyatomic interferences are
suppressed. Although any gas introduced to the cell can be considered
a collision gas as long as the ions don't chemically react with it, helium
appears to be the most effective gas for KED as will be discussed in
Section 3.4, and has been most often used in collision cell ICP-MS. For
more than a decade after the first introduction of collision/reaction
cell ICP-MS, pure He collision gas had been used in limited ICP-MS
systems. Now that all the collision/reaction ICP-MS instruments
commercially available provide “KED mode” using 100% He gas, KED
has undoubtedly become a standard technique. The KED technique
was already discussed in 2002 as one of the means to control the
appearance of the secondary reaction products in the comprehensive
review of collision/reaction cell ICP-MS by S. D. Tanner et al. [4] Howev-
er, the kinetic energy range considered in their paper (up to a several
eV) differs from that in the He collision cells of the current ICP-MS
instruments (up to ca. 20 eV), which is adopted for efficient reduction
of plasma-derived polyatomic ion interferences. To the best of the
author's knowledge, accurate, scientific, quantitative description of
KED that reflects the current He collision cells is missing in literature.
For better use of this technique, the operation principles and the limita-
tions of KED in collision cell ICP-MS are described in this paper.
To delineate how KED works for polyatomic interference reduction,
it is imperative to know ion kinetic energies both for the atomic analyte
ions and the polyatomic interfering ions in the cell. An ion, before it
collides with a gas molecule, starts traveling in the cell with the kinetic
energy determined by some instrumental conditions, and after
experiencing multiple collisions it exits the cell with reduced kinetic
energy due to those collisions. At the cell exit, however, the analyte
ions of interest have to maintain as much kinetic energy as to overcome
the potential barrier. Therefore the cell needs to operate under non-
thermal conditions (the ion kinetic energy is above the thermal kinetic
energy of the collision gas). In the non-thermal energy range considered
here (from ca. 20 eV to a few eV), the collision can be regarded as that
between two billiard balls (hard spheres) rather than as that caused
by the electrical interaction between the charge (ion) and the dipole
(neutral gas molecule). Then the ion kinetic energy after collisions is es-
timated using the hard sphere collision model, which will be discussed
together with the cell conditions for the non-thermal operation.
The ion's traveling direction may be altered by collision. The scatter-
ing angle, the angle between the ion velocity vectors before and after
the collision, is also given by the hard sphere collision model. If they
are large in non-thermal conditions, the ions are likely to scatter out
of the ion guide. For ions having masses sufficiently higher than collision
gas, however, the ion's scattering angle will be shown to be small
enough for the ion to be confined within the ion guide.
As for KED in reaction cell ICP-MS, the analyte atomic ions have to
retain sufficient kinetic energy after unreactive collisions with the cell
gas to overcome the energy barrier, while cell-formed product ions
are blocked by the barrier and the signal intensities of the plasma-
based interfering ions are reduced through chemical reactions with
the cell gas. In this regard hydrogen may be the most usable reaction
gas [5,6], since it has small mass to minimize the loss of the analyte
ion's kinetic energy and has the sufficient reactivity toward the interfer-
ing argon and some argide ions. The operation of non-thermal reaction
cell will be described, shedding light on the kinetic energy of reactant
(interfering) ions as well as non-reactive analyte ions. As an example
of KED for reaction cell ICP-MS, the kinetic energy of 40Ca+ (analyte)
after collisions with H2 and the degree of reduction of 40Ar+
(interferent) through reaction with H2 are estimated to see how much
improvement of signal-to-background ratio can be achieved.
2. Collision processes in the cell
2.1. Decrease of ion kinetic energy by collision
In the current non-thermal collision cells operated with KED, the
bias voltage of the multipole ion guide is typically set to −16 V [7] or
slightly more negative [8], by which ions are accelerated to ca. 20 eV
of kinetic energy upon entering the ion guide as will be discussed in
the next section. With this rather high kinetic energy, however, an ion
could not be transmitted if it entered the ion guide with the velocity
having a large angle to the ion guide axis, because the ion kinetic energy
in the radial direction became too high for the ion to be confined within
 N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44
the ion guide by the multipole RF field. Only a well-collimated portion
of the ion beam that is incident on the ion guide entrance will be trans-
mitted, hence should be taken into account here. Then, the initial ion
velocity in the cell can be considered to be in the axial direction.
The ion travels along the central axis of the ion guide as it oscillates
in the radial direction and/or rotates around the central axis. In the
multipole RF ion guide used in collision cell ICP-MS, there is usually no
electrical field in the axial direction. In such cases, the ion travels at a
constant axial velocity until it collides with a gas molecule. In other
words, the ion has the constant axial kinetic energy before the first
collision. The initial kinetic energy (the kinetic energy of the ion after
entering the ion guide but before the first collision) is typically ca.
20 eV as mentioned above, which is determined by some instrumental
factors as described in the following section. Consider an ion, atomic
or polyatomic, that does not react or dissociate in the event of a collision.
After traveling some distance from the ion guide entrance, it collides
with a gas molecule. Compared to the ion velocity, the gas molecule is
much slower since it has only thermal kinetic energy at about room
temperature (about 30 meV). Hence it can be considered that the ion
collides with a stationary target. Just like the collision of two billiard
balls, one moving, one at rest, the moving ion slows down after impact,
imparting its kinetic energy to the stationary gas molecule. Subsequent-
ly, the ion travels farther at the reduced speed until it collides with the
next gas molecule where it slows further. Thus the kinetic energy of
the ion decreases step-by-step through multiple collisions. The final
kinetic energy of the ion (the ion kinetic energy in the axial direction
at the exit of the ion guide) depends on the initial ion kinetic energy;
the loss of ion kinetic energy caused by a collision event; and the num-
ber of collision events that the ion experiences in the ion guide.
2.2. Initial ion kinetic energy
For the ions extracted from the Ar plasma into the vacuum, the ion
energy is, in the absence of an applied field, given by [9,10]
mi 5
E0 ¼ V p þ kB T 0 ð1Þ
mAr 2
where Vp is the DC plasma potential. The second term (mi/mAr)(5/2)kBT0
is the kinetic energy that the ion acquired through gas expansion in the
sampler–skimmer interface, where mi and mAr are the masses of the ion
and an argon atom, respectively; kB is the Boltzmann constant; and T0 is
plasma gas kinetic temperature. Assuming the interface is grounded, the
ion kinetic energy is equal to E0 when the ion travels in a region of zero
potential. The ion is accelerated when it enters a region of lower poten-
tial, that is, the ion kinetic energy increases when the potential where it
travels decreases. Thus, the ion kinetic energy equals to E0 minus the
potential at the ion's position. In the cell, the averaged potential is deter-
mined by the DC bias voltage applied to the ion guide. The kinetic
energy before collisions (the initial kinetic energy), Ei is then expressed
as
Ei ¼ E0 −V guide ð2Þ
where Vguide is the DC potential of the ion guide. When the DC bias
voltage (rod offset voltage) of the ion guide is set to −20 V for example,
the singly charged positive ions gain about 20 eV of kinetic energy, since
the average potential of Vguide ≈ −20 eV is established around the cen-
tral axis of the ion guide where the ions travel. An As+ ion (mi = 75u),
for instance, has the initial kinetic energy Ei of 24 eV for Vp = 2 eV, T0 =
5000 K and Vguide = − 20 eV. The first collision occurs with the ion
kinetic energy of Ei. It should be noted that the kinetic energy in the
radial direction that the ion acquires from the ion guide RF field is
much smaller than Ei in this energy range, as will be shown by the ion
trajectory simulation in Section 2.5, and therefore can be ignored as
long as the ion is not thermalized.
33
2.2. Number of collisions in the cell
We consider an ion traveling at non-thermal velocity in the cell
where there are stationary gas molecules at a number density of n.
The average distance the ion travels between two collisions, known as
the mean free path, is given by (σn)−1, where σ is the collision cross
section for the collision between the ion and the gas molecule [10,11].
Then the average number of collision events N, that the ion experiences
in the cell is given by the ion's traveling path length in the cell L, divided
by the mean free path.
N ¼ σ nL ð3Þ
N depends on the distance the ion travels but not the time it spends in
the cell as we consider ions traveling through the space where there
are stationary gas molecules. Under typical cell conditions (non-thermal
conditions), the traveling path length L is approximately equal to the
axial distance that the ion covers, that is, the ion guide length. As will
be shown in the Section 2.5, the ion's oscillating and rotating motions
contributes little to the entire path length of the ion in the non-
thermal cell, because the non-thermal atomic analyte ions reach the
cell exit before oscillating or rotating as many times as their path length
is affected by such motions.
For an atomic ion colliding with a He atom, σ is on the order of 10−19
to 10−18 m2 [12], which corresponds to the collision diameter (bmax) of
0.2 to 0.5 nm when treating the ion and the He atom as hard spheres. In
the hard sphere collision model, bmax is the sum of the radii of the two
collision partners, ri + rg (see Fig. 1), which is related to the collision
cross section as
2
2
σ ¼ πbmax ¼ π r i þ r g : ð4Þ
Among the different definitions of atomic radii (e.g. covalent radii,
and ionic radii), van der Waals radii are most appropriately employed
to estimate collision cross sections, since they reflect the closest
approach of two non-bonded atoms. They have been proposed for
neutral atoms of most elements [13], e.g. 0.143 nm for He and
0.188 nm for As. Taking the van der Waals radii of He and As as the
hard sphere radii of a He atom and an As+ ion, respectively, the cross
section for the collision between them, for example, is calculated from
Eq. (4) to be 3.3 × 10− 19 m2. (It should however be noted that the
size of a positive ion may be smaller than that of the corresponding
neutral atom because the electron cloud is contracted toward the nucle-
us by the excessive protons when the atom is ionized. Therefore, for the
collision between a positive ion and a neutral gas molecule, the hard
sphere cross section estimated from van der Waals radii may be some-
what larger than the empirically measured cross section. Having said
that, van der Waals radii are used for the discussion in this paper since
the absolute values of cross sections are not essential in polyatomic
interference reduction, but the difference of the cross sections between
the atomic and polyatomic ions is of essence as will be discussed
later).
For the polyatomic ions occurring in ICP-MS, the collision cross
sections are not well known. However, when comparing the size of a
polyatomic ion with the atomic ion of the same mass (e.g. ArO+ vs
Fe+, ArCl+ vs As+, Ar+ +
2 vs Se ), the former is expected to have a larger
collision cross section than the latter due to the fact that the interatomic
distance (bond length) of the polyatomic ions occurring in ICP-MS is
nearly as large as the radii of the constituent atoms. For example, the
bond lengths of ArO+, ArCl+ and Ar+ 2 are 0.167 nm, 0.208 nm and
0.252 nm, respectively [14]. The van der Waals radii of the constituent
atoms, Ar, O and Cl, are 0.183 nm, 0.150 nm and 0.182 nm, respectively
[13], although they would be somewhat smaller when they form
polyatomic ions. If compared with the size of the atomic 75As+ (ri ≈
0.188nm), the size of the polyatomic 40Ar35Cl+ is apparently much
34 N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44

mi mi
v’i
bmax=ri + rg
vi α

b θ/2
mg
β b mg
vg=0 v’g
At Impact

Fig. 1. Collision between a moving sphere (mi) and a stationary sphere (mg) viewed in the laboratory frame of reference.

larger. Hence, in general, a polyatomic ion experiences more collisions molecule) as illustrated in Fig. 1. The laboratory frame scattering
than the isobaric atomic ion due to its larger cross section. angles of the ion and the gas molecule, α and β, respectively, are
The gas number density n is proportional to the flow rate of the cell related to θ in the forms of
gas (typically 0.1 to 10 sccm), and inversely proportional to the total
area of the openings at the entrance and exit of the cell. When effusive sinθ
tanα ¼ ð9Þ
flow through the openings is assumed, it is given by [10] mi =mg þ cosθ

4F
n¼ ð5Þ
vg A sinθ
tanβ ¼ ð10Þ
1− cosθ
where F is the number of gas molecules flowing into the cell per unit
 1=2
time; vg is the average speed of the cell gas molecules vg ¼ 8kBT
πmg ; where α ranges from 0 to π, and β from 0 to π/2, being independent
and A is the area of the cell openings (the entrance and exit apertures of ion kinetic energy.
of the cell). For a cell operating at room temperature with the two Consider how the impact parameter b affects the ion kinetic energy
openings of 2 mm in diameter, n is about 1.1 × 1021 m− 3 after collision and the ion scattering angle. When the ion collides head-
(pressure = 4.7 Pa) at a He flow rate of 5 sccm. In this case, the average on with a stationary gas molecule (b = 0, θ = π, α = 0 or π, β = 0), the
number of collision events in a 0.1 m long ion guide is at least about ion loses maximum energy, continuing forward or bouncing back de-
10 (σnL = 10−19 m2 × 1.1 × 1021 m−3 × 0.1 m). The variance of pending on the ion mass relative to the gas molecule mass. When the
the number of collisions that each ion experiences in the cell will be two particles graze one another (b ≈ bmax, θ ≈ 0, α ≈ 0, β ≈ π/2),
discussed in Section 3.3. the ion loses almost no energy (E ' i ≈ Ei), and keeps moving in the
original direction. For an As+ ion (mi = 75u) colliding with a stationary
2.3. Kinetic energy and scattering angle after a collision He atom (mg = 4u), the calculated kinetic energies after the collision
and scattering angles of the two particles are shown in Fig. 2 as a
pffiffiffi
Base on the hard sphere collision model, the kinetic (translational) function of θ (as a function of b). At b ¼ bmax = 2 (the mean impact pa-
energies of the ion and the gas molecule after a single collision E ' i rameter, which gives θ = π/2), for example, Eq. (6) gives E ' i = 0.904 Ei,
and E ' g, respectively, are given by [15] that is, 9.6% of the As+ kinetic energy is lost by the collision. At the mean
impact parameter, the scattering angle α is close to the maximum when
1 m 2 þ mg 2 þ 2mi mg cosθ mi N mg, which is, however, only 3.1° for As+ ions colliding with He.
E0 i ≡ mi v0i ¼ Ei i
2

2 ð6Þ
2 mi þ mg Therefore the axial component of the As+ velocity after collision
remains dominant, allowing us, to a first approximation, to ignore the
radial component produced by the collision with He.
1
E0 g ≡ mg v0g ¼ Ei −E0i
2
ð7Þ
2 2.4. Ion kinetic energy after multiple collisions

The final kinetic energy Ef, the kinetic energy of the ion after all the
where Ei is the ion kinetic energy before the collision, which is the
collisions experienced in the cell, is then given by
initial kinetic energy given by Eq. (2) if the collision is the first one
in the cell; mg is the mass of the gas molecule; and θ (0 ≤ θ ≤ π) is
the scattering angle in center-of-mass coordinates. In these equa-
N mi 2 þ mg 2 þ 2mi mg cosθ j
E f ¼ Ei ∏
2 ð11Þ
tions, the kinetic energy (velocity) of the gas molecule before the j¼1 mi þ mg
collision is assumed to be zero as it is considered as a stationary
target. In the hard sphere collision, θ is related to the impact param-
where
eter b in the form of


θ b θ j ¼ 2 cos−1 b j =bmax ð12Þ
cos ¼ ð8Þ
2 bmax

The impact parameter b (0 ≤ b ≤ bmax) is the extrapolated distance and bj is the impact parameter at the jth collision, N is the number of col-
between the incoming ion's path and the center of the target (gas lisions that the ion experienced in the cell. A rough estimate of the final

Normalized Impact Parameter b/bmax
Kinetic Energy after Collision
1 0.97 0.87
1 90
normalized by Ei
0.8
E'i/Ei
0.6
E'g/Ei
0.4
0.2
0 0
0 30 60
Center-of-Mass Scattering Angle θ
Fig. 2. Kinetic energies after collision (left) and scattering angles in the LAB frame (right) calculated for As+ and He as a function of b, assuming that As+ collides elastically with a stationary
He atom.
energy can be made assuming all the collisions occur at θj = 90° (at the
mean impact parameter). With this assumption Eq. (11) is rewritten
as
( )N
m 2 þ mg 2
E f ¼ Ei
i 2
mi þ mg
For an As+ ion that enters the ion guide with Ei = 24eV and experi-
ences 10 collisions with He gas, the Ef of the As+ is 24eV × 0.90410 =
8.7eV. The interfering polyatomic ion ArCl+ (mi = 75u) enters the ion
guide with about the same initial kinetic energy as As+ (see Eq. (2)),
but collides with He more times than As+ because of its larger collision
cross section. Assuming the cross section is twice as large as that of As+,
an ArCl+ experiences 20 collisions on average in the pressurized cell
where an As+ experiences 10 collisions on average. The final kinetic en-
ergy of the ArCl+ after 20 collisions is estimated from Eq. (13) to be
24eV × 0.90420 = 3.2eV, which is significantly lower than that of the
As+ that experienced 10 collisions. Thus an axial kinetic energy differ-
ence is produced between the two isobaric ion species at the exit of
the ion guide. Then with the post-cell potential barrier that is higher
than 3.2 eV but lower than 8.7 eV, the ArCl+ ions are blocked while
the As+ ion are allowed to transmit through the quadrupole mass filter
that is set to select m/z = 75. It should be noted that polyatomic ions
may lose more kinetic energy than expected from this hard sphere
collision (elastic collision) model, because the part of collision energy
can be deposited into the internal energies such as vibrational and rota-
tional ones. Therefore the kinetic energy difference between the atomic
and polyatomic ions of the same mass may be somewhat greater than
what is estimated from this model.
If the collision gas flow rate is increased to induce many more colli-
sions, the kinetic energies of As+ and ArCl+ will both damped to the
thermal energy of the collision gas, resulting in no difference between
their kinetic energies. If the ion guide bias is made less negative for
better ion transmission, the ions will have a higher tendency to be ther-
malized by collisions due to their lowered initial kinetic energy, leading
to a smaller difference in the final kinetic energies between the two iso-
baric ion species. For example, if the ion guide bias is increased to −1 V
[16,17], the lowered initial kinetic energy of As+ and ArCl+ (ca. 5 eV)
results in the smaller difference of final kinetic energies, 1.8 eV for
As+ and 0.67 eV for ArCl+, which would make efficient KED difficult
as will be discussed in Section 3.2. Therefore both the gas flow rate
and the ion guide bias are the important factors in producing sufficient
kinetic energy difference. Of course it is desirable to minimize (thermal-
ize) the kinetic energy of the interfering polyatomic ions, but the cell has
to be in a non-thermal condition for the analyte ions to retain sufficient
kinetic energy so that they can overcome the potential barrier after the
cell.
N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44 35
Normalized Impact Parameter b/bmax
1 0.97 0.87 0.71 0.50 0.26 0
Scattering Angle[o] (Lab Frame)
0.71 0.50 0.26 0
80 α
As+ 70 β
60 He
50
40
30
He 20
10 As+
90 120 150 180 0 30 60 90 120 150 180
[o] Center-of-Mass Scattering Angle θ [o]
It should be noted that the transmission of relatively low mass ions
through the pressurized cell to the mass filter is low due to their large
energy loss and scattering loss. The kinetic energy loss, or the energy
transfer to the target gas molecule, is large when the relative difference
between the ion mass and the gas molecule mass is small, which is the
ð13Þ case for low mass ions in collision cell ICP-MS (Imagine that complete
transfer of kinetic energy occurs when a moving hard sphere collides
head-on with a stationary hard sphere of the same mass). For example,
Eq. (6) indicates that the 35%, 46% and 41% of the kinetic energy of Li+
(7u) are lost via a single collision with H2 (2u), He (4u) and NH3
(17u), respectively at the mean impact parameter (Li+ doesn't react
with any of these gases). With such large kinetic energy loss per
collision, the analyte Li+ is nearly thermalized after several collisions
as predicted from Eq. (13) and hence unable to surmount the potential
barrier after the cell. The scattering angles α of Li+ calculated by Eq. (9)
are 16°, 30° and 68° for a collision with H2, He and NH3, respectively, at
the mean impact parameter. With such large scattering angles, a signif-
icant fraction of the post-collision kinetic energy can be in the radial
direction. Assuming the velocity of a Li+ ion before collision is in the
axial direction, the radial components of the post-collision kinetic ener-
gy are (sin 16°)2 = 7.6 %, (sin 30°)2 = 25 %, ( sin 68°)2 = 86 % of the
total post-collision kinetic energy, respectively (note that kinetic energy
is proportional to the square of speed). Due to these large radial compo-
nents of post-collision kinetic energy, which are in the non-thermal
energy range, the likelihood of the ion scattering out of the ion guide
is high. For these reasons, even for non-reactive cell gases, signal loss
of low mass ions is significant when the non-thermal cell is operated
with KED.
2.5. Ion trajectories in non-thermal cells
Now that the ion velocity (speed and direction) after collision can
be obtained from Eqs. (6) and (9), ion trajectories through the RF ion
guide in the pressurized cell can be simulated by statistically selecting
the position where collision occurs and the impact parameter for each
collision [15]. The length of the trajectory in the ion guide corresponds
to the ion's traveling path length L in the cell that determines the num-
ber of collisions. Examples of calculated trajectories of the m/z = 75 ion
colliding with He atoms in an octopole and a quadrupole are shown in
the Fig. 3. The operating conditions of the two ion guides used for the
calculations are summarized in Table 1, which are probably typical for
the cells used in ICP-MS [18].
Without He in the ion guide, the calculated trajectories (black lines)
indicate constant amplitude and period of the oscillatory motion (with
more rapid but much smaller wiggles superimposed, which correspond
to the radio frequencies of the voltage applied to the ion guides). In the
octopole (upper), the ion, having the axial kinetic energy of 24 eV, oscil-
lated only 2.1 times with amplitude of 1 mm during the passage through
36 N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44

Z-X plane Without He With He Octopole Ion Guide leading to a longer traveling path in the ion guide. However, as shown
by the red trajectories, along which the ion underwent 20 collisions,
the ion oscillated slightly more times in the octopole (2.3 times) or 2
3.6mm more times in the quadrupole (5.5 times) during the passage through
the ion guide. And the amplitude of oscillation slightly decreased
Traveling direction
toward the ion guide exit, which reflects an effect of collisional focusing
100mm [15], though the effect is small due to the limited number of collisions
X-Y plane with the light gas (He) for non-thermal operation of the cell. The final
Z-Y plane kinetic energy was calculated to be 4.1 eV both in the octopole and
quadrupole, confirming the non-thermal conditions were maintained
after 20 collisions with He gas. The lengths of the trajectories are
100.5 mm and 127.0 mm in the octopole and quadrupole, respectively,
which are the same as or slightly longer than those without collisions,
but still close to the ion guide length. Under non-thermal conditions
ions reach the ion guide exit before oscillating so many times as the
oscillatory motion contributes to the total path length. Therefore, the
Z-X plane Without He With He Quadrupole Ion Guide ion's traveling path length in the ion guide is about the same as the
ion guide length in the non-thermal cell, which justifies the discussion
in Section 2.2 to estimate the number of collisions.
8.2mm

3. KED in collision cell ICP-MS

Traveling direction
125mm X-Y plane 3.1. Potential barrier

Z-Y plane In KED mode, the potential barrier is set up by the quadrupole
mass filter that is DC biased at a voltage higher than the ion guide bias
voltage. The ion has the axial kinetic energy Ef at the exit of the ion
guide that is biased at a DC potential Vguide as described in Section 2.4.
The (total) ion energy is Ef + Vguide, the sum of the kinetic and potential
energies. Once the ion has left the cell, the ion energy is conserved (until
it hits the detector), assuming that no collision occurs outside the cell.
In the quadrupole mass filter biased at a DC potential Vquad, the axial
Fig. 3. Examples of ion trajectories calculated with and without He gas in an octopole
kinetic energy of the ion passing through the mass filter Equad is
(upper) and a quadrupole (lower) ion guide. The black trajectories are calculated without
collision (without He). The initial conditions were chosen so that the trajectories are determined by the energy conservation equation, Equad + Vquad =
within the Z–X plane. Using the identical initial conditions, the red trajectories are Ef + Vguide. Namely,
calculated with He collisions. The black dots on the red trajectories indicate where


collision occurs. The blue straight lines represent the innermost position of the rod surface Equad ¼ E f  V quad  V guide ð14Þ
of the multipole ion guides. Note that the scale in the radial direction is expanded to show
oscillatory motions of the ion. (For interpretation of the references to color in this figure
legend, the reader is referred to the web version of this article.) Therefore, if the potential difference (barrier height) Vquad − Vguide is
smaller than Ef, the ion is able to pass through the mass filter with a
certain axial velocity since Equad N 0. Otherwise it is blocked at the
the entire ion guide of 100 mm in length. Similarly, in the quadrupole entrance of the mass filter by this potential barrier. For example, when
(lower), the ion oscillated about 3.5 times with amplitude of c.a. 1 mm the mass filter is DC biased at − 15 V (Vquad ≈ − 15eV) and the ion
while traveling the axial distance of 125 mm. The lengths of the trajec- guide at − 20 V (Vguide ≈ − 20eV), the potential barrier of 5 eV is set
tories are calculated to be 100.5 mm and 126.5 mm in the octopole and up at the entrance of the mass filter. As discussed in 2.4, the As+ ions
quadrupole, respectively, indicating that the ion path length in the ion that have experienced 10 collisions have the Ef higher than 5 eV on
guide is approximately the same as the ion guide length. If He gas is in- average. Therefore, they surmount the barrier and travel through the
troduced to the ion guides, the ion slows down through collisions. mass filter set to m/z = 75, while the ArCl+ ions, which have Ef of
Therefore it oscillates more as it spends more time in the RF ion guide, only about 3.2 eV on average, are blocked. Obviously, if the potential
barrier is too high or too low, both analyte and interfering ions are
blocked or allowed to pass, resulting in no effective interference
reduction.
Table 1
Ion guide used for ion trajectory simulation. 3.2. Efficiency of KED
Octopole RF-only Quadrupole RF-only
ion guide ion guide Even if the potential barrier is properly set up, the efficiency of kinet-
Length [mm] 100 125
ic energy discrimination is not 100% — some of the interfering poly-
Inscribed diameter [mm] 3.6 8.2 atomic ions surmount the barrier and some of the atomic analyte ions
Frequency of voltage [MHz] 11 2.5 are blocked by the barrier or ejected by the quadrupole fringe field
RF amplitude [V] 180 200 [19]. There are two factors that limit the efficiency of KED; 1) the non-
m/z of ion 75 75
ideal energy filtering property of the potential barrier, and more impor-
Ion mass [u] 75 75
Initial kinetic energy 24 24 tantly, 2) the spread of the final energy caused by the statistical nature
(axial) [eV] of the collision processes.
Initial position 1 mm off the central axis 1 mm off the central axis Although it is easy and simple to use the quadrupole mass filter as a
Cell gas No gas or He No gas or He potential barrier, it does not have an ideal energy-filtering property,
Number of collisions 0 or 20 0 or 20
that is, 100% transmission for the ions that have Equad N 0. Slow ions
 N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44
(Equad ≈ 0) are likely to be ejected by the fringe field of the quadrupole,
even if they have sufficient kinetic energy to overcome the potential
barrier. As will be discussed in the next section, the ions have a spread
of final kinetic energies. Even if the average final energy is well above
the barrier height, a portion of ions having lower kinetic energy may
be unable to pass through the fringe field, leading to the loss of analyte
ion signals. In addition, the spreads of the final energies for the atomic
analyte ions and polyatomic interfering ions may result in an overlap
of the energy distributions of these two ion species, that is, a portion
of analyte ions and that of interfering ions have the same final kinetic
energy. This incomplete energy separation hinders efficient KED. To
what extent the polyatomic ions are suppressed and the atomic analyte
ions are blocked by KED is discussed in the next section.
3.3. Energy spread caused by multiple collisions
Unlike billiards games, occurrence of gas phase collisions is deter-
mined by the laws of probability. Even for the same ion species, the
number of collisions that each ion experiences in the cell is not constant.
Additionally the kinetic energy loss per collision is not constant either,
as it depends on impact parameter b, which can't be controlled as a
good pool player controls it to obtain the desired velocity of the balls
after the collision. Therefore, the ions reaching the cell exit will have a
spread of final kinetic energy. Take an extreme but good example
here. The probability of an ion experiencing N collisions in the cell,
P(N) is given by the Poisson distribution as
ðσnLÞN −σ nL
P ðN Þ ¼ e ð15Þ
N!
where σnL is an average number of collisions that the ions experience
in the cell (see Eq. (3)). When the cell is pressurized to the extent
that σnL = 10 for As+, 45 out of one million As+ ions pass the cell with-
out a single collision, since P ð0Þ ¼ e‐10 ¼ 4:5  10−5. These 45 lucky As+
ions retain the initial kinetic energy. When it is 24 eV, the population of
As+ ions will have a final kinetic energy distribution extending up to
24 eV while the average final energy is 8.7 eV as discussed in Section
2.4. The same is true for the interfering ArCl+, some of which will
have higher final energy than their average final energy. Fig. 4 shows
the probability distributions of the number of collisions for σnL =
10 and 20 calculated from Eq. (15). Only 12.5% of the ions go through
10 collisions for σnL = 10, while the rest experience more or fewer
collisions than the average number of 10. The variation of the number
of collisions that ions undergo is one of the factors that produce a spread
of the final ion kinetic energy.
Examples of final kinetic energy distributions calculated using
Eq. (6) are shown in Fig. 5. For each of 100,000 ions of mass 75u travel-
ing through a He-filled cell, statistical calculation of a traveling distance
0.14
σnL=10
0.12
σnL=20
0.10
Probability P(N)
0.08
0.06
0.04
0.02
0.00
0 10 20 30 40
number of collisions N
Fig. 4. Probability distribution of the number of collisions for the average collisions of 10
and 20 calculated from the Poisson distribution.
37
between collisions was repeated until the ion covers the entire length of
the ion guide and the impact parameter for each of the collisions was
statistically selected to determine the post-collision kinetic energy[15].
The initial kinetic energy was assumed as Ei = 24eV with no energy
spread (the mono-energetic ions entering the cell). Fig. 5a shows histo-
grams of the final kinetic energies of 100,000 ions calculated under the
conditions of σnL = 10 and 20, intending to emulate the energy distri-
butions of As+ and ArCl+, respectively. The average final energies for
σnL = 10 and 20 were calculated from the distributions to be 8.69 eV
and 3.26 eV, respectively, which were coincident with the rough esti-
mate of the final energies obtained from Eq. (13). Of the 100,000 ions,
the ions having a final energy lower than 5 eV were 8646 for σnL =
10 (As+) and 81,879 for σnL = 20(ArCl+). Therefore, by the 5 eV poten-
tial barrier set up for KED, 8.65% of the As+ signal is lost, but 81.9% of the
ArCl+ interference is removed. If this level of interference reduction is
insufficient for samples containing high Cl matrix, one should increase
the potential barrier height or the He flow rate (increase the He density
n). Fig. 5b shows the final energy distributions when the He flow rate is
doubled (σnL is 20 for As+ and 40 for ArCl+). In this condition, the
ions having final energy lower than 5 eV were 81,879 for σnL = 20
(As+) and 99,994 for σnL = 40(ArCl+), which means that despite
81.9% loss of the As + signal, the ArCl + interference is reduced by
more than four orders of magnitude (reduced from 100,000 to
6) by the 5 eV KED. At this high He flow rate, one may want to recover
the As+ signal by reducing the barrier height. However, ArCl+ inter-
ference would increase more rapidly than the As+ signal. For exam-
ple, by reducing the barrier height from 5 eV to 3 eV the As+ signal
loss decreases from 81.9% to 46.8% as indicated in Fig. 5b, while the
number of the ArCl+ ions surmounting the barrier increases from 6
to 153 (by more than 20 times), eventually leading to degradation
of the S/B ratio. The potential barrier height for KED, set with a com-
promise between the analyte signal level and the degree of interfer-
ence reduction, is also an important factor to determine the collision
cell performance in addition to the collision gas flow rate and the ion
guide bias.
3.4. Ion signal dependence on collision gas density (gas flow rate) of
different collision gases
In order to select the appropriate collision gas flow rate, the im-
provement of S/B ratio has been estimated by measuring the signals of
atomic analyte ion (analyte standard sample) and polyatomic interfer-
ing ion (matrix blank) as a function of the flow rate [8]. The ions that
overcome the potential barrier contribute to the ion signal observed in
collision cell ICP-MS with KED. The number of collisions N that gives
the ion the final energy higher than the barrier height, Vquad − Vguide,
is obtained from the following condition, assuming all the collisions
occur at the mean impact parameter (see Eq. (13)).
!N
m 2 þ mg 2
E f ≡Ei
i 2 NV quad −V guide ð16Þ
mi þ mg
For example, N is lower than 21 for the As+ ions (mi = 75 [u], Ei =
24eV) colliding with He (mg = 4 [u]) when the barrier height Vquad −
Vguide is set to 3 eV, that is, the As+ ions that have experienced 20 or
fewer collisions overcome the barrier and are transmitted to the detec-
tor, and those that have experienced more than 20 are blocked by the
barrier. The fraction of the As+ ions that are detected corresponds to
the sum of the probabilities of the ion experiencing from zero to 20
collisions. Therefore, in general, the ion signal (intensity of the ions
that overcomes the barrier) is given by
XNc X
Nc
ðσ nLÞN −σ nL
I=I0 ¼ P ðN Þ≡ e ð17Þ
N¼0 N¼0
N!
38 N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44

6000 120000
σnL=20 a

cumulative number of ions

5000 100000
number of ions
4000 80000
σnL=10
3000 60000

2000 40000

1000 20000

0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Final Ion Kinetic Energy Ef [eV]

36000 120000
σnL=40 b

cumulative number of ions

30000 100000
number of ions

24000 80000

18000 60000

12000 40000

6000 σnL=20 20000

0 0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
Final Ion Kinetic Energy Ef [eV]

Fig. 5. Final kinetic energy distributions of the 100,000 ions of mass 75u that have traveled through the collision cell pressurized with He gas to the extent that the average collisions (σnL)
are 10 for As+ and 20 for ArCl+ (a); and 20 for As+ and 40 for ArCl+ (b) (It is assumed the collision cross section of ArCl+ is twice larger than As+). The horizontal energy scale is divided
into bins of 0.2 eV width. Scaled on the right Y axis are the cumulative numbers of ions for the two different σnL (circles and triangles). These cumulative distributions, shown as a function
of Ef, represent the total number of ions having the energy lower than Ef.

where I0 is the intensity of the ions exiting the collision cell, I is the
intensity of the ions exiting the cell that overcome the barrier, P(N) is
the probability of the ion experiencing N collisions given by the Poisson
distribution Eq. (15), and Nc is the maximum number of collisions that
gives the ion the final energy higher than the barrier height. As the
collision gas density n (flow rate) increases, the average number of
collision (σnL) increases, resulting in the decrease of the probability of
the ion experiencing a smaller number of collisions. Therefore the ion
signal decreases with the flow rate. Fig. 6a shows the normalized signals
of the ions (mi = 75u) that overcomes the barrier as a function of He
number density, calculated using Eq. (17) for Nc = 20, mi = 75 [u],
and L = 0.1 [m]. The collision cross section was assumed to be σ =
3.3 × 10− 19 m− 2, the value derived from the van der Waals radii of
He and As atoms (see Section 2.2). For comparison, the calculations
were also performed for the cross sections 1.5 and 2 times larger to
emulate signals of the polyatomic interfering species. At n = 8 × 1020
[m− 3], for example, the signal of the ion with σ = 3.3 × 10−19 m− 2
(atomic analyte) decreases by one order of magnitude, while the signals
of the ions having 1.5σ and 2σ (polyatomic interferences) decrease by
3 and 7 orders of magnitude, respectively, which corresponds to
the S/B improvement of 2 to 6 orders of magnitude. Obviously, the
greater the difference of collision cross sections, the higher the S/B
improvement.
For comparison the same calculations were performed for other
collision gases, Ne and Ar, as shown in Fig. 6b and c, respectively. Nc is
6 for Ne and 3 for Ar, which are far fewer than 20 for He. This is because
the loss of ion kinetic energy per collision is larger for heavier gas. It is
clearly seen that the relative signal intensities of the ions of larger
cross sections (polyatomic ions), compare to those of smaller cross
sections, are higher for heavier gases, indicating that the polyatomic in-
terference reduction by KED is less effective when using heavier colli-
sion gas. This result is solely derived from the characteristics of the
Poisson distribution as it is obtained from Eq. (17) alone. Efficient KED
against polyatomic ions can be achieved at a high average number of
collisions, which is possible with light collision gas.
The curves in Fig. 6a, b and c, concave downwards on a semi-log
graph, are in sharp contrast to the exponential decay (linear decay on
a semi-log graph) of the ions reduced by the reaction with the cell gas
as will be shown in Section 4.4. However, the measured ion signals
often deviate from these profiles due to the collisional focusing and
scattering loss.
3.5. KED against doubly charged ions
Doubly charged ions act as interfering ions against certain
singly charged analyte ions. For example 150Nd++ and 150Sm++
interfere with 75As+, because these doubly charged ions have the
same m/z(=75) as a singly charged arsenic ion. Unfortunately doubly
charged ion interference cannot be suppressed by the collision cell oper-
ating with KED. This section clarifies the reason, which seems to have
long been misunderstood [20].
Using Eqs.(1) and (2), the initial kinetic energy of a (singly charged)
analyte ion in the cell is expressed as
mi 5
Es ¼ V p þ kT 0 −V guide ð18Þ
mAr 2
where mi is the mass (not m/z) of the analyte ion. Likewise, the initial ki-
netic energy of the doubly charged interfering ion, which has the mass
of 2mi, is given by
2mi 5
Ed ¼ 2V p þ kT 0 −2V guide ð19Þ
mAr 2
The initial kinetic energy of the doubly charged interfering ion is
exactly twice higher than the singly charged analyte ion of the same
 N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44 39

1.E+01 charged ions. Then do doubly charged ions overcome a high potential
normalized signal intensity I/I0 a barrier that singly charged ions cannot because of their higher kinetic
1.E+00
energy? Is this why KED does not work for reduction of doubly charged
σ ion interferences? It is not. The potential barrier height for the doubly
1.E-01
charged ions to overcome is also twice higher than for singly charged
1.E-02 ions. For example, with the DC bias voltage of the ion guide in the cell
1.5 σ set to − 20 V and that of the quadrupole after the cell set to − 15 V,
1.E-03 the potential barrier height Vquad − Vguide is ca. 5 eV for singly charged
ion since the potential energies in the ion guide and quadrupole are
1.E-04
2σ about Vguide = −20 eV and Vquad = −15 eV, respectively as discussed
1.E-05 in the Section 3.1. The barrier height for doubly charged ions is ca.
10 eV because the potential energies of the doubly charged ions are
1.E-06 doubled (Vguide = −40 eV and Vquad = −30 eV). Therefore, with both
mi=75 [u], mg =4 [u]
kinetic energy and barrier height doubled, doubly charged ions have
1.E-07
the same “difficulty” in overcoming the barrier as singly charged ions
0 2E+20 4E+20 6E+20 8E+20 1E+21
have.
-3
He number density [m ] What about the kinetic energy loss induced by collision? There is
difference in the energy loss between singly and doubly charged ions
1.E+01 of the same m/z since it is mass-dependent as indicated by Eq. (6). For
b example, as has been discussed before, the kinetic energy of As+
1.E+00
normalized signal intensity I/I0

(mi = 75u) after collision with a He atom (mg = 4u) at the mean
1.E-01 σ impact parameter (cos θ = 0) is given by Eq. (6) as Ei′ = 0.904 Ei,
which means 9.6% of the kinetic energy that the As+ has before the
1.E-02 collision is lost. For an interfering Nd++ ion (mi = 150u) that collides
1.5 σ with He in the same condition (cos θ = 0), the equation gives E ' i =
1.E-03 0.949 Ei. The kinetic energy loss is 5.1%, which is smaller than As+. As
intuitively understood from a hard sphere collision event, heavier ions
1.E-04
2σ lose less kinetic energy than lighter ions at the collision with a light
1.E-05 gas molecule.
The final energy after multiple collisions should then be examined,
1.E-06 which depends on the number of collisions (or collision cross section).
mi =75 [u], mg =20 [u] Using Eq. (13), the conditions for the singly charged analyte to over-
1.E-07
come the barrier (Vquad − Vguide) and for the doubly charged interfering
0 1E+20 2E+20 3E+20 4E+20
ion to be blocked by the same barrier (2Vquad − 2Vguide) are given by
-3
Ne number density [m ]
!σ 1 nL
mi 2 þ mg 2
Es
2 NV quad −V guide ð20Þ
1.E+01 mi þ mg
c
normalized signal intensity I/I0

1.E+00 !σ 2 nL
4m 2 þ mg 2
1.E-01 σ 2Es
i 2 b2V quad −2V guide ð21Þ
2mi þ mg
1.E-02
where σ1 and σ2 are the collision cross sections for the singly and doubly
1.5 σ
1.E-03 charged ions, respectively (σ1nL and σ1nL are the average numbers
of collisions for the singly and doubly charged ions, respectively). Com-
1.E-04 bining the above two conditions leads to the single condition,
2σ
1.E-05 σ 2 ln C 1
N ð22Þ
1.E-06 σ 1 ln C 2
mi=75 [u], mg =40 [u]
1.E-07 where
0 1E+20 2E+20 3E+20
m 2 þ mg 2
Ar number density [m-3] C1 ¼
i 2 ð23Þ
mi þ mg
Fig. 6. Normalized signals of the ions (mi = 75u) that surmount the 3 eV potential barrier,
calculated as a function of He gas number density (a), Ne gas number density (b) and Ar 4mi 2 þ mg 2
gas number density (c). The DC bias potential of the ion guide in the cell is
C2 ¼
2 ð24Þ
2mi þ mg
Vguide = −20 eV (The initial kinetic energy is 24 eV). The calculations were carried out
for three collision cross sections, 3.3 × 10−19 m2 (solid lines denoted by σ),
5.0 × 10−19 m2 (dotted lines denoted by1.5σ) and 6.6 × 10−19 m2 (dashed lines denoted In the case of 150Nd++ (or 150Sm++) interference on 75As+, the
by 2σ). The maximum numbers of collisions that allow the ion to surmount the barrier are condition of σ2/σ1 N 1.93 is derived for He collision gas. Namely, the col-
20, 6, 3 for He, Ne and Ar, respectively. The difference of cross sections results in difference
lision cross section of Nd++ has to be at least 1.93 times larger than that
of ion signal intensities, which is larger for lighter collision gas.
of As+ in order to selectively block Nd++ by the potential barrier. The
cross sections can be estimated from the radii of the collision pairs,
m/z (Ed = 2Es). This is because the kinetic energy that the doubly Nd++–He and As+–He as discussed in Section 2.2. The van der Waals
charged ions acquire in the gas expansion and the potential energy radii of neutral As and Nd are 0.188 nm and 0.295 nm [13] respectively.
that they have in a potential field are doubled compared with singly Assuming that ionic As+ and Nd++ have the same radii, 0.188 nm and
40 N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44

0.295 nm, respectively (most optimistic assumption), the cross section
of the Nd++–He pair, calculated from Eq. (4), is still only 1.75 times
larger than that of the As+–He pair. Therefore, the above requirement
(Eq.(22)) for selective discrimination against Nd++ will not be met.
Note that when Nd is ionized to be doubly charged, the electron cloud
shrinks to a greater degree than when As+ is ionized to be singly
charged. Hence the σ2/σ1 must be smaller than 1.75.
When an As+ ion enters the ion guide with the initial kinetic energy
of 24eV and experiences 10 collisions with He gas on average, a Nd++
ion enters the ion guide with 48eV and its average number of collisions
is 18 (1.75 times the As+ collision number) at most. In this case the final
kinetic energy of the As+ is 24eV × 0.90410 = 8.7eV and that for the
150
Nd++ is 48eV × 0.94918 = 18.7eV on average. When the potential
barrier height is set to 19 eV to block the interfering Nd++ ions, the
barrier height for As+ is 9.5 eV (the half of 19 eV), which is too high
for the 8.7 eV As+ ions to surmount. It is readily understood from this
example that KED does not work for doubly charged ion interferences
because the kinetic energy of the doubly charged ion does not decrease
sufficiently through collisions due to its heavier mass.
4. KED in reaction cell ICP-MS
which the ion reacts is also examined, as it is one of the important factors
to determine the reaction efficiency of the cell, which is energy-
dependent. Finally, taking up an example of 40Ar+ interference on
40
Ca+, a loss of the analyte ion (40Ca+) signal due to KED and a reduc-
tion of the interfering ions (40Ar+) through the reaction with H2 is
theoretically calculated under the conditions given in Table 2.
4.2. Reactant ion intensity in the cell
The following bimolecular reaction is assumed to occur in the cell.
Aþ þ B→C þ þ D ð25Þ
where A+and B are the reactants — the interfering ion and the cell gas
molecule, respectively. Using the reaction rate constant k, the reaction
rate (reduction rate of A+) is then expressed as
 
d Aþ  
¼ −k Aþ ½B ð26Þ
dt

4.1. Non-thermal reaction cell The density of the cell gas in the cell, [B], can be considered constant
while the reactions are proceeding, since it is usually orders of magni-
In reaction cell ICP-MS, KED solely serves to reduce the interference tude higher than the ion density [A+] in the cell. In an ideal thermal
caused by in-cell product ions, as many of these product ions have reaction cell, k can also be treated as a constant value as it depends
kinetic energies nearly as low as the thermal energies in the cell [3], only on the cell gas temperature that determines the kinetic energy
and therefore can be selectively discriminated against by the potential with which the reaction (reactive collision) occurs. The ion density
barrier if the analyte ions exit the cell with sufficient kinetic energy to [A+] is then obtained by integrating the above equation as
surmount the barrier. In other words, the analyte ions should not
 þ  þ
react with the cell gas and have to retain sufficient kinetic energy after A ¼ A 0 expð−k½Bt Þ ð27Þ
unreactive collisions with the cell gas. (Obviously KED can't be applied
to the mass-shift method [21], where the product ions that are deliber-
where [A+]0 is the initial ion density before reaction, t is the reaction
ately produced from the reaction with the analyte ions are measured at
time. However, for a non-thermal reaction cell, where the ion kinetic
a new m/z to circumvent the original interference). The original inter-
energy in the cell is determined by the instrumental parameters, the
fering ions, produced in the plasma, are reduced through the reaction
energy-dependent rate constant k has to be used, which is defined
with the cell gas. In order to achieve a desired degree of interference
as[23]
reduction, a high reaction gas density (flow rate) may be necessary,
which will contradict the need to maintain the kinetic energy of the
analyte ions. In this regard, hydrogen gas is preferred [5] because the k ¼ vσ r ð28Þ
gas molecule is light enough to minimize the ion kinetic energy loss
caused by collision and have sufficient reactivity for some plasma- where v is the relative speed of the colliding pair (A+ and B), which is
based interferences, e.g. Ar+ and Ar+ 2 [22]. The potential barrier height
approximately the speed of the reactant ion A+ in the non-thermal
has been typically set to about 3 eV in H2 reaction cell ICP-MS, seemingly cell as was discussed in Section 2.1, and σr is the reaction cross section,
an empirically compromised value, as we have observed that lowering which is also energy-dependent (a function of v).
the barrier height leads to the increase of in-cell product ion signals, In the non-thermal cell, the ions travel in the axial direction as
while increasing the barrier height causes the decrease of analyte ion they collide (and react) with the reaction gas molecules. Therefore
signals.
In a non-thermal reaction cell filled with reaction gas, each of the
interfering ions that have entered the cell travels a certain distance
Table 2
with the initial kinetic energy and then collides with a gas molecule.
Parameters and constants used for calculations.
At this collision each ion may or may not react with the gas. If it reacts,
the interference of one ion is eliminated. If it does not, it will travel Value Comment
farther and collide with another gas molecule at a slightly reduced Initial kinetic energy 21.1 eV Ion guide bias of −18 V
velocity, where, again, the reaction may or may not occur. Individual of 40Ca+ and
40
ions repeat collisions until they react with the gas or until they reach Ar+, Ei
Potential barrier 3 eV Quad mass filter bias of −15 V
the cell exit. A fraction of the reactant ions will reach the cell exit height
(without reaction), which corresponds to the reduced interference H2 number density 0.95 × 10 21 −3
m Calculated from Eq. (5) for a typical
signal (background signal) observed in the reaction cell ICP-MS. in the cell, n operating condition (e.g. H2 flow
For better understanding of KED in reaction mode, the intensity of rate of 6sccm)
Ion guide length, L 0.1 m
the interfering ions (reactant ions) at the cell exit is first derived for
Collision cross section 2.83 × 10−19 m2 Reference [16]
non-thermal reaction cells, and then their kinetic energy is calculated of Ar+ (and Ca+)
to examine whether they are able to surmount the barrier. As will be for H2, σ
discussed in Section 4.3, the kinetic energy of the reactant ions differs Reaction cross section 2 × 10−19 m2 Reference [27] and references
from that of non-reactive analyte ions (the latter can be estimated in of Ar+ for H2, σr therein, the value at ion kinetic
energy of 20 eV
the same way as described in Section 2.4). The kinetic energy with
 N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44 41

the reactant ion density decreases from the entrance to the exit of This equation expresses the Lambert–Beer law. [A+]0 and [A+] are now
the cell. Taking dt as the time taken for the ion to travel a short dis- considered to be the reactant ion intensities at the entrance and exit of
tance dz (dz = vdt), and using Eq. (28), Eq. (26) is rewritten as the cell, respectively. The equation indicates that the ion intensity
  decays exponentially as the cell gas density n (flow rate) increases.
d Aþ  
¼ −σ r Aþ ½B ð29Þ
dz
4.3. Kinetic energy of reactant ions in the cell
As will be shown in Section 4.3, σr is approximately constant at any
position in the cell for the gases having relatively high reactivity and low The kinetic energy of reactant ions in the cell pressurized with
mass. In such cases the above equation can be integrated from the cell reaction gas is considered here based on hard sphere collision model.
entrance (z = 0) to the cell exit (z = L). First, the kinetic energy of the reactant ions at the cell exit is derived to
 þ  þ discuss whether the interfering (reactant) ions that have survived the
A ¼ A 0 expð−σ r nLÞ ð30Þ reaction cell can be discriminated by the energy barrier after the cell.

mi Ei

ri

rg

mg

Collision Cross Section

Ei
mi

ri

rg

Target for reaction mg

Reaction Cross Section

Fig. 7. Collision/reaction geometry between the ion (mi) and the gas molecule (mg).
42 N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44

Second, the kinetic energy that the reactant ion has when it reacts is
estimated, which determines the reaction cross section.
It is assumed that the hard sphere collision cross section σ and the
reaction cross section σr are known for the ion–gas molecule pair.
If every collision leads to reaction, σr is equal to σ, which means that
the ion always reacts whenever it collides with a gas molecule. This is
however not the case with usual ion-molecule reactions even if they
are exothermic without activation energy, because the occurrence of
reaction is affected by the kinetic energy with which the two reactants
collide with each other. Therefore σr is smaller than the collision cross
section σ, and is energy-dependent. Hence, the cross section for the
unreactive collision is given by σ − σr, which corresponds to the gray
area in Fig. 7. The average number of unreactive collisions in the cell is
then give by
N ¼ ðσ −σ r ÞnL ð31Þ
For Ar+ in H2 reaction cell, N is calculated to be 7.9 using the physical
constants listed in Table 2. Note that the probability of an Ar+ ion
experiencing no collision (the fraction of Ar+ exiting the cell with no
collision at all) is estimated from Eq. (15) as exp(−σnL) = e−27.17 =
1.59 × 10−12. The fraction of Ar+ exiting the cell without reaction is
estimated from Eq. (30) as exp(− σrnL) = e−19 = 5.6 × 10−9, which
is much higher than the probability of no collision at all. Therefore,
most of the Ar+ ions exiting the cell (without reaction) have experi-
enced some collisions in the cell, thereby lost a part of their initial kinet-
ic energy.
The kinetic energy after (unreactive) collision depends on the im-
pact parameter b as discussed previously (the smaller the impact pa-
rameter, the smaller the post-collision kinetic energy). Fig. 7 implies
that reaction occurs when the impact parameter is small, and unreactive
collision occurs when it is large. Compared with a non-reactive pair
(σ N 0, σr = 0), between which (unreactive) collisions occur at any
impact parameter lower than bmax, unreactive collisions between the
reactive pair (σ N σr N 0) may tend to occur at relatively larger impact
parameters on average, that is, at impact parameters larger than the
pffiffiffi
mean impact parameter b ¼ bmax = 2 that was given to the collisions
between non-reactive pairs as discussed in Sections 2.3 and 2.4. For
the sake of simplicity of discussion, however, this mean impact param-
eter is used as a typical impact parameter for the unreactive collisions
between the reactive pair to calculate the ion kinetic energy. Then
using Eqs. (13) and (31), the ion kinetic energy after all the unreactive
collisions experienced in the cell can be expressed as
( )ðσ−σ r ÞnL
mi 2 þ mg 2
E f ¼ Ei
2 ð32Þ
mi þ mg
and that of the reaction not occurring (unreactive collision) is
(σ − σr)/σ. Therefore, the probability of the ion reacting at the jth
collision is given by
σ−σ  j−1 σ
r r
P r ð jÞ ¼ ; j ¼ 1; 2; 3… ð33Þ
σ σ
Fig. 8 shows Pr(j) calculated for three different values of σr/σ. For
σr/σ = 0.9 (highly reactive gas), the probabilities of reaction occur-
ring at the first, second and third collision are 90%, 9% and 0.9%,
respectively. Therefore, within the first few collisions most of the
reactant ions react, which is true whether the cell is thermal or
non-thermal. For less reactive gas, the probability of reaction occur-
ring at later collision becomes higher, and the reaction cross section
at the later collisions may be different from that at the early colli-
sions due to the ion kinetic energy reduction caused by the preceding
unreactive collisions. For the reaction between Ar + and H2 (σ r /
σ ≈ 0.7), 97% of the Ar+ ions that have entered the cell react with
H2 within the first three collisions. Although σr is dependent on ion
kinetic energy, therefore, changes as the ion undergoes unreactive
collisions, it can be approximated by the constant value at the initial
kinetic energy, as will be discussed next.
As the probability of reaction at each collision is given by Eq. (33),
the average kinetic energy of the ion at the reactive collision is calculat-
ed as
X
∞
Er ave ¼ E j P r ð jÞ ð34Þ
j¼1
where Ej is the ion kinetic energy at the jth collision, which is the kinetic
energy after the ion experiences (j − 1) unreactive collisions. Using
Eq. (13), it is approximately given by
( ) j−1
m 2 þ mg 2
E j ¼ Ei
i 2 ð35Þ
mi þ mg
Eq. (34) indicates that the average kinetic energy at which the ions
react with the gas molecules, Er ave is determined by the initial ion
kinetic energy, the masses of the reactants (ion and gas), the collision
cross section and the reaction cross section. Since the reaction cross
section σr is energy-dependent, Er ave and σr are mutually dependent.
Therefore the two quantities should be determined self-consistently.
For Ar+ in H2 reaction cell under the conditions shown in Table 2, the
average kinetic energy of Ar+ ions at the reaction is estimated from
Eq. (34) to be 20.3 eV, which is close to the initial kinetic energy of
1
Probability of reaction at the jth collision

0.9 r/

For 40Ar+ in H2 reaction cell under the conditions shown in Table 2, 0.8 r/
the final kinetic energy Ef is calculated to be 0.90937.9 Ei = 9.96eV, r/
0.7
which is much higher than the typical height of the barrier set up after
the cell. Compared with the analyte isobar Ca+, the finale energy 0.6
of Ar+ is higher. Note that the average number of collisions with H2 0.5
that a non-reactive Ca+ ion undergoes (σnL) is higher than that of 0.4
unreactive collisions that an Ar+ ion undergoes ((σ − σr)nL). The Ar+
0.3
ions having reached the cell exit, which have the kinetic energy of
9.96 eV, are able to surmount the potential barrier and eventually will 0.2
strike the detector as the background signal. Hence, the reduction of 0.1
Ar+ signal is solely due to the reactions with H2, not due to KED. 0
The kinetic energy with which the interfering ions react with gas 0 1 2 3 4 5 6 7 8 9 10
molecules can be estimated by calculating the probabilities of the ion j
reacting at the jth collision, where j = 1, 2, 3… For the ion that collides
with the gas molecule, the probability of the reaction occurring is the Fig. 8. The probability of a reactant ion not reacting at any collision before the jth collision
ratio of the reaction cross section to the collision cross section, σr/σ, but then reacting at the jth collision. σr is assumed to be constant.
 N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44 43

21.1 eV. In this calculation, the reaction cross section at ca. 20 eV was and the other charge transfer, both of which are exothermic, but the
used and it is consistent with the calculated ion kinetic energy of former is dominant in the energy range considered here [27].
20.3 eV. Since most Ar+ ions react with H2 within the first few collisions
and the kinetic energy loss by unreactive collision is small for light H2 Arþ þ H2 →ArHþ þ H ð37Þ
gas, the kinetic energy with which Ar+ reacts is approximated by its
initial kinetic energy, and hence the reaction cross section at that energy Arþ þ H2 →Ar þ H2 þ ð38Þ
can be applied to the reactions at any position in the cell, and at any H2
density (H2 flow rate). This should be also the case with other reactant Using the (total) reaction cross sections σr for these reactions, the
ions that have high reactivity toward H2, e.g. Ar+ +
2 , ArH [24] and ArO
+ Ar+ signal is expressed as (see Section 4.2),
[25].
½Arþ  ¼ ½Arþ 0 expð−σ r nLÞ ð39Þ
+ +
4.4. Ar and Ca signals in H2 reaction cell ICP-MS
where [Ar+]0 and [Ar+] are the Ar+ intensities at the entrance and exit
of the cell, respectively; n is the H2 gas density, L is the cell length. Then,
As an example, theoretically reviewed in this section is 40Ar+
if σr is known, the Ar+ signal intensity can be estimated. For the above
interference on 40Ca+, which was reported to be reduced by H2 gas
two reactions (37) and (38), the reaction cross sections have been
to an extent of a single ppt level of BEC for calcium in non-matrix
thoroughly investigated as a function of Ar+ kinetic energy [27]. The
samples [26]. Typical operating conditions for Ca+ measurement in H2
average kinetic energy of Ar+ with which it reacts with H2 in the cell
mode are listed in Table 2, together with physical constants involved
was estimated to be 20.9 eV in the previous section. At around this
there.
kinetic energy the reported reaction cross sections for Eqs. (37) and
The loss of Ca+ due to KED is estimated in the same way as described
(38) are 1 to 2 × 10−19 m2 and 0.5 to 1 × 10−19 m2, respectively (The
in Section 3.4 by regarding H2 as collision gas of mg = 2[u]. With the
values vary from literature to literature) [27]. The sum of the two
initial 40Ca+ kinetic energy of Ei = 21.1eV, the number of collisions N
cross sections corresponds to σr in Eq. (39), which is approximately
that gives the Ca+ the final energy higher than the barrier height is
σr ≈ 2 × 10− 19 m2. Now that σr, n and L are all known, the degree
obtained from Eq. (16). For a potential barrier of 3 eV in height, N is
of Ar+ reduction [Ar+]/[Ar+]0 is calculated from Eq. (39) to be
calculated to be 20 or lower for 40Ca+. Therefore, using Eq. (17), Ca+
5.6 × 10− 9. Taking into account of the decrease of the Ca+ signal by
signal intensity ICa is given by
one order of magnitude due to KED as discussed above, the net
improvement of S/B ratio is 0.1/(5.6 × 10−9) = 1.8 × 107. Under
X
20
ðσ nLÞN normal plasma conditions without cell gas the modern quadrupole
ICa =ICa0 ¼ e−σnL ð36Þ
N¼0
N! ICP-MS systems give 40Ar+ intensity of about [Ar+]0 = 1010 cps and
Ca+ signal of about 100,000 cps/ppb. Then with H2, the 40Ar+ intensity
is reduced to [Ar+]0 × 5.6 × 10−9 cps (ca. 60 cps), while the Ca+ is to
where ICa0 is the Ca+ intensity of all energies after the cell, which corre- 10,000 cps/ppb, resulting in BEC of 6 ppt.
sponds to the Ca+ signal observed without H2 in the cell or without KED
after the cell. At the H2 density n given in Table 2, the average number of 5. Summary
collisions (σnL) that a Ca+ ion experiences with H2 in the cell is 27. At
this average number, ICa/ICa0 is calculated to be ca. 0.1, indicating that It has been more than a decade since the collision/reaction cell ICP-
90% of the Ca+ are blocked by the barrier and 10% are detected. Ca+ MS became an essential technique in many analytical laboratories. In
signal intensity as a function of H2 number density n, calculated using this period, “the KED mode” was established as a simple and easy
Eq. (36), is shown in Fig. 9 together with Ar+ signal intensity, which approach to operate the cell-based ICP-MS for interference reduction.
will be derived next. However an accurate, quantitative description of the KED approach
To estimate the signal intensity of the reactant Ar+ ions, two types of has not been presented. Using the hard sphere collision model, the
reaction with H2 should be considered. One is H-atom transfer reaction collision/reaction cells operated with KED under non-thermal condi-
tions were depicted as accurately as possible to clarify the basic princi-
ples and limitations of this technique. They are summarized as follows.

1.E+01 1) Through multiple collisions with gas molecules in the collision

cell, a significant difference of the average kinetic energy is pro-
1.E+00
normalized signal intensity I/I0

Ca+ duced between the ions of the same mass that have different
1.E-01 collision cross sections. At the cell exit, the kinetic energy of the
ion species having a larger cross section is lower than those hav-
1.E-02
ing a smaller cross section, because the former experience more
1.E-03 collisions than the latter on average. With a potential barrier set
1.E-04 up after the cell, the former can be blocked while the latter is
Ar+ allowed to transmit to the detector. This is the basic principle
1.E-05
for polyatomic ion interference reduction by KED, based on the
1.E-06 premise that the polyatomic ions have a larger cross section
1.E-07 than the isobaric atomic analyte ions.
2) Due to the statistical nature of collision events, multiple collisions
1.E-08 produce a spread of kinetic energy even for the same ion species.
1.E-09 Hence, the kinetic energy distributions of the atomic analyte ions
0 2E+20 4E+20 6E+20 8E+20 1E+21 1.2E+21 and of the interfering polyatomic ions partly overlap each other.
H2 number density [m-3] The intrinsic limitations of KED lie in this incomplete separation of
the kinetic energies.
Fig. 9. Normalized signals of the 40Ca ions that surmount the 3 eV potential barrier as a
3) In order to achieve greater separation of the kinetic energies of the
function of H2 gas number density and of the 40Ar ions after the cell. The DC bias potential analyte and interfering ions, the initial kinetic energy has to be
of the ion guide in the cell is Vguide = −18 eV. high enough to prevent atomic analyte ions from being thermalized
44 N. Yamada / Spectrochimica Acta Part B 110 (2015) 31–44
by the multiple collisions. For this reason, the DC bias voltage of the
ion guide in the cell is often set to more negative (typically ca.
−20 V) than the optimum for ion transmission.
4) It was theoretically shown that lighter collision gas is more effective
than heavier one for polyatomic ion reduction by KED. This is also
due to the statistical nature of collision processes.
5) KED against doubly charged interfering ions does not work due to
their higher mass than the singly charged analyte ions.
6) In non-thermal reaction cell ICP-MS, KED is used to suppress the
signals derived from in-cell formed ions. The signals of (unreactive)
analyte ions are decreased by KED due to their lowered kinetic ener-
gies through the multiple collisions with the reaction gas. For this
reason, light gases, specifically H2, are favored.
7) In H2 reaction cell ICP-MS, when the reaction cross section approxi-
mates the collision cross section, KED does not contribute to the
reduction of plasma-based interfering ions, which are reduced solely
through the reaction processes in the cell.
Acknowledgment
The author thanks Professor Akbar Montaser (the George Washington
University) for motivating him to write up this review, and Steven Wilbur
(Agilent Technologies) for his invaluable advice on the manuscript.
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