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39 (2006) 937–943

JOURNAL OF PHYSICS D: APPLIED PHYSICS doi:10.1088/0022-3727/39/5/007

**The time-dependent development of electric double-layers in saline solutions
**

R Morrow, D R McKenzie and M M M Bilek

Applied and Plasma Physics, School of Physics, University of Sydney, Sydney, NSW 2006, Australia E-mail: r.morrow@physics.usyd.edu.au

Received 26 September 2005, in ﬁnal form 15 December 2005 Published 17 February 2006 Online at stacks.iop.org/JPhysD/39/937 Abstract We have studied the time-dependent development of electric double-layers (ionic sheaths) in saline solutions by simultaneously solving the sodium and chlorine ion continuity equations coupled with Poisson’s equation in one dimension. The study of the effects of time-varying electric ﬁelds in solution is relevant to the possible health effect of radio-frequency electric ﬁelds on cells in the human body and to assessing the potential of using external electric ﬁelds to orient proteins for attachment to surfaces for biosensing applications. Our calculations, for applied voltages of 10–175 mV between the electrode and the solution, predict time scales of ∼0.1–110 µs for the formation of double-layers in solutions of concentration between 0.001 and 1.0 M. We develop an empirical equation that can predict the double-layer formation time to within 10% over this wide parameter range. The method has been validated by comparing the solutions obtained, once the program has run to a steady state, with the standard non-linear Poisson–Boltzmann equations. Excellent agreement is found with the Gouy–Chapman solution of the non-linear Poisson–Boltzmann equation. Thus the method is not restricted in accuracy and applicability as is the case for the linear Poisson–Boltzmann equation. The method can also provide solutions for cases where there are orders of magnitude changes in the ion densities; this has not been the case for previous studies where small perturbation analysis has been employed. The method developed here can readily be extended to two and three dimensions using time-splitting methods.

1. Introduction

The application of steady electric ﬁelds to solutions containing macromolecules is used in the electrophoresis process to separate molecules according to their molecular weight. In this paper, we address the problem of evaluating the electric ﬁeld as a function of time after the application of a potential difference to two electrodes separated from the solution by a very thin insulating layer. Such an analysis is of interest, for example, in determining the effects of environmental electromagnetic ﬁelds on cellular molecules at various frequencies. Another motivation is to study the effect of time-varying electric ﬁelds on proteins in saline solutions with the aim of modifying the rate of adsorption of proteins to surfaces and the orientation of the adsorbed proteins.

0022-3727/06/050937+07$30.00 © 2006 IOP Publishing Ltd

Electrostatic interactions between biological molecules in saline solutions have generally been evaluated using the Poisson–Boltzmann equation; this gives the static equilibrium electric ﬁelds with reasonable accuracy [1,2]. Very frequently the Poisson–Boltzmann equation is linearized to eliminate exponential terms making the equation more convenient to solve [3]. The linearized Poisson–Boltzmann equation is often called the Debye–H¨ ckel equation [1, 3], and the Debye u length [4] appears as one of the coefﬁcients. Both the linear and non-linear forms of the Poisson–Boltzmann equation give similar and adequate descriptions of steady-state electrostatic solutions for saline solutions but cannot account for the effect of an externally applied time-varying electric ﬁeld. Thus, we aim to evaluate the time scales for the formation of doublelayer ion sheaths and the time scales for, and magnitudes of, 937

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our work is distinct in that we develop a criterion for deﬁning the formation time for the double-layer based on a correlation coefﬁcient and then derive an empirical equation to describe the formation time as a function of both salt molarity and applied voltage. Equations (1) and (2) are solved simultaneously with Poisson’s equation: ∂ 2φ e =− (ρNa − ρCl ). respectively. and include chemical reactions. Finally.1. Hence we obtain the characteristic times for the formation of the double-layer sheath as a function of the ion concentration and applied voltage. to give the time evolution of the ion density distributions and the electric ﬁeld distribution. we must solve the continuity equations for the drift and diffusion of sodium and chlorine ions. change the number and character of the ionic species included. such that WNa = µNa E and WCl = µCl E. respectively. and DNa and DCl are the sodiumion and chlorine-ion diffusion coefﬁcients. In this way we obtain new ion density distributions with only slight incremental changes.2. The numerical algorithm developed by Tankovsky and Syrakov [9] uses only ﬁrst-order discretization in space and will be subject to the error of numerical diffusion. We apply type (1) boundary conditions at electrode interfaces with the solution and type (2) boundary conditions at points in the bulk solution far from the inﬂuence of the electrodes. O’Brien and White [5–8]. 12]. These effects are readily included using our techniques of directly solving the relevant differential equations and would be difﬁcult to implement using the methods of Hunter. this is not the case for our ﬂux-corrected transport method which is fourth-order in space and time [11. µ. We wish to include the following effects: 1. 2. and O’Brien [8] are all small perturbation analyses of the relevant equations and are of limited relevance to the cases we wish to study where the ion densities change by orders of magnitude. we outline the continuity equations used to obtain the time-dependent development of double-layers. (1) ∂ρCl ∂x (2) where t is the time. In a recent paper Tankovsky and Syrakov [9] describe phenomena similar to those described in this paper. Also. respectively. However. In order to retain the degree of ﬂexibility required. (5) . We continue the timedependent calculations until the solution no longer changes and compare the results with the Gouy–Chapman solution. and the penetration of the electric ﬁeld into the solution is analysed. so that charges build up on the electrode surface and no charges ﬂow through the boundary and (2) a boundary in the solution where the ion densities are held constant by the movement of ions in the bulk solution. we must follow the changes in the ion drift velocities due to new electric ﬁelds obtained by solving Poisson’s equation with the new net charge density. O’Brien and White [6. We then introduce the Gouy–Chapman solution of the non-linear Poisson–Boltzmann equation which is used to validate our approach and provide an end point for deﬁning the formation time for the double-layer. 3. It is assumed that the transport properties of ions in the solution are determined for constant room temperature conditions giving constant diffusion coefﬁcients. 2. Continuity equation approach for time-dependent analysis In order to obtain time-dependent solutions for the ion number density distributions. and the potential and electric ﬁeld. coupled with Poisson’s equation. D. . 938 2. The electric ﬁeld. evaluate the time history of the electric ﬁeld anywhere in the body of the solution. and we develop an empirical formula that describes these characteristic times. is then computed using E=− ∂φ . 7]. Two types of boundary conditions are applied: (1) a thin perfect insulator covering a metal electrode at a ﬁxed potential. where E is the electric ﬁeld and µNa and µCl are the sodium-ion and chlorine-ion mobilities. and ion mobilities. we present results for a saline solution between two electrodes that are insulated so that double-layer ion sheaths develop at both electrodes. and the potential is ﬁxed. ρNa and ρCl are the sodium-ion and chlorine-ion number densities. and we present the time history of the electric ﬁeld in the centre of the solution.R Morrow et al electric ﬁelds penetrating the solution before the formation of the double-layer ion sheaths. using a small time-step. The continuity equations for sodium ions and chlorine ions are as follows: ∂ρNa ∂(ρNa WNa ) ∂ =− + ∂t ∂x ∂x ∂(ρCl WCl ) ∂ ∂ρCl =− + ∂t ∂x ∂x DNa DCl ∂ρNa ∂x . 2 ∂x ε r ε0 (3) where εr is the relative permittivity and ε0 is the permittivity of free space. E. ∂x (4) 2. we simultaneously solve the individual continuity equations for sodium ions and chlorine ions. we compute the external circuit current waveform for a realistic applied voltage waveform with a ﬁnite rise and fall time. Note that we ﬁrst make these comparisons with the Gouy–Chapman equation for a simple saline solution in order to validate the method. e is the electron charge and φ is the electric potential. evaluate the response current generated in the external circuit by a given applied voltage waveform. Theory In this section. The Gouy–Chapman equation The Poisson–Boltzmann equation [3] which describes the steady state potential distribution in the saline solution is deﬁned as ∂ 2φ eρ0 eφ =− exp − ∂x 2 εr ε0 kB T − exp + eφ kB T . x the distance from the anode. Previous studies of the time-dependent formation of a double-layer by Hunter [5]. change the boundary conditions. WNa and WCl are the sodium-ion and chlorineion velocities. respectively. such as from conducting to non-conducting. Simultaneously. 4.

and hence W . d the gap between the electrodes. For the present calculations a very ﬁne mesh is used with the minimum x = 0.304M −1/2 nm. (11) where M = [NaCl] is the molarity of the saline solution in moles per litre. Here Va is the applied voltage. and lightning [15] calculations and has been shown to introduce negligible numerical dispersion or numerical diffusion. κ (10) A convenient expression for the Debye length. kB is Boltzmann’s constant and T is the solution temperature. (14) where V is the applied voltage. neglecting fringe effects. For the long calculations required. is deﬁned as [3.1 µs and the pulse width is 10 µs. The boundary conditions used for the ions at an electrode are non-conducting boundary conditions where ions ﬂow to and from the boundary. An analytic solution of equation (5) is the Gouy–Chapman solution deﬁned as [3] φ= where γ = tanh(eφ0 /4kB T ) and κ= The electric ﬁeld is given by E=− ∂φ = − 8ρ0 kB T /εr ε0 sinh(eφ/2kB T ). For example.8 GHz Pentium PC.01 M solution it takes ∼20 000 time steps to follow the development of the double-layer for 3. taking 124 s on a 2. The rise and fall time chosen for the voltage impulse is 0. streamer [14].5{erf[(wP − c − t)/wr ] − erf[(wP − c − t)/wr ]}. are simulated. with ∼106 time-steps. t must be evaluated after every time-step on the entire mesh and the minimum value used. Thus a waveform with a ﬁnite rise and fall time. The time-step for the calculations is limited by the Courant–Friedrics–Levy condition for stability [16] given by t x . ∂x (9) 2e2 ρ0 .1. 3. the non-conducting electrode boundary conditions as speciﬁed above are applied.Development of electric double-layers where ρ0 is the average density of both sodium and chlorine ions in the solution. but take ∼600 000 time steps. wP is the half-width of the pulse. The pulse is computed using V = 0.2. wr is the half-width of the rise time and fall time of the pulse and c is the time to the centre of the pulse from the start of the calculation. the calculations indicate that it actually takes a long time to get close to the ideal Gouy–Chapman solution. with 100 mV applied voltage between the electrode and 0. 12]. where t is the time-step. ﬂowing in the external circuit due to the formation of a double-layer sheath is given by the Morrow– Sato equation [10] which can be simpliﬁed [10] for the case of small gaps where A d 2 to give I= A e d d 0 ρNa WNa − ρCl WCl + DNa ∂ρNa ∂ρCl − DCl dx ∂x ∂x ∂Va +εr ε0 .45 µs. The problem of deﬁning convergence is addressed in this paper and is not simple. The use of the Morrow–Sato equation [10] allows the capacitive current to be included to give the true total external current due to a voltage impulse applied to a solution. the ions do not ﬂow through the boundary or emanate from the boundary.1λD near the boundary where the electric ﬁeld.8 GHz Pentium PC. The calculation of the external circuit current due to double-layer formation The current. are large. (12) ∂t Note that CG = Aεr ε0 /d is the capacitance of the gap. The continuity equations The numerical method used to solve the continuity equations is an implicit ﬂux-corrected transport method described in detail elsewhere [11. Calculations of the development of the double-layer at 0.01 M for 50 µs are extremely close to the ideal Gouy– Chapman solution. 2. an anode and a cathode. Impulse voltage waveform It is not realistic to apply a square voltage wave that is absolutely sharp since such waveforms cannot be applied in practice and may cause unrealistic results in the calculations. λD . For most of the calculations in this paper an anode electrode boundary and a boundary point in the solution are used. hence t is generally small and many time steps are necessary. The solution obtained after 3. For the example of a solution where two electrodes. x is the mesh size and W is the ion drift velocity. it is crucial to use a very accurate numerical algorithm as used in this paper. A the cross-sectional area of the electrodes. W (13) The Debye length. the errors randomize rather than accumulate. Numerical methods 3. taking 5 s on a 2. εr ε 0 k B T (8) (7) 2kB T 1 + γ e−κx . ln e 1 − γ e−κx (6) corona [13]. 939 3.3. I .45 µs is close to the Gouy–Chapman results but not fully converged. at room temperature. This method has been used for very long calculations in gas discharges for . and rounded corners has been developed for these calculations. At the boundary in the solution the ion density is kept constant to represent ion densities maintained by ions from a large body of solution beyond the boundary point in the solution. is [4] λD = 0. The error function erf is available as a function in Fortran and other computer languages and is also available in tabulated form [17]. 4] λD = 1 .

. After 4 µs r = 0. expanding exponentially away from the electrode to a point in the solution 500 nm from the electrode. Very similar results were obtained over the full range of concentrations from 0. After 3 µs the solution is close to the Gouy–Chapman solution (ﬁgure 2) indicating that the system is already close to the equilibrium state.0 50. A potential of +100 mV is set at the electrode.0 and 50 µs after the start of the calculations showing the development of the ion distributions with time in a 0. The net result is a build-up of negative charge leading to a rising electric ﬁeld at the electrode.01 M saline solution.0 M). at x = 0 m. For these calculations. Similar results were obtained using the same applied voltage of +100 mV over the entire saline molarity range considered (0.5 and the temperature T = 298 K. after 10 µs r = 0. εr = 78.) We have calculated the correlation coefﬁcient. 19]: µNa = µCl = 7. the electric ﬁeld is derived from φj via numerical differentiation using equation (4) which may introduce unnecessary errors.91 × 10−8 m2 V−1 s−1 and DNa = DCl = 2. the electric ﬁeld in the centre of the saline solution goes steadily to zero over the simulated time. the cathode is at zero volts and the voltage waveform deﬁned in section 3. r.98. The time elapsed since the application of the +100 mV bias for each curve in microseconds is shown in the ﬁgure.1λD . τ . For the calculation where two electrodes are considered. It can be seen that the sodium ions move away from the anode and the chlorine ions move towards the anode as the calculation proceeds. in these calculations. Figure 2 shows the ﬁeld distribution in the bulk solution as a function of time while ﬁgure 3 shows an enlarged view of the ﬁelds near the electrode.2 is used. The development of the electric ﬁeld distribution near the electrode. The anode is set at x = 0 m and the cathode at x = 1. The time-dependent solution Results are presented for the development of the double-layer ion sheath at the anode for a 0. unless otherwise stated.0 Ion Number Density (m-3) 10 26 0. 5.0 10 23 0 5 10 15 X (nm) Figure 1. Physical data In order to make a direct comparison with the Gouy–Chapman equation we have taken the sodium and chlorine mobilities and diffusion coefﬁcients to be the same as the values for chlorine [18.1 10 25 10 24 0.1. Figure 1 shows the time evolution of the sodium ion and chlorine ion distributions at three time instances after the application of a +100 mV bias at the insulated electrode. and zero potential at the solution boundary. is deﬁned with an initial spacing at the electrode of dxj +(1/2) = 0.05 10 0 0 5 X (nm) 10 15 Figure 2. It is then possible to set a criterion that objectively deﬁnes a relaxation time. Because of the asymptotic approach of r → 1 a criterion must be set to deﬁne a measure of the relaxation time.99 998. A potential of +100 mV is applied at an electrode at X = 0 while the X = 16 nm boundary is held at zero potential. The computational mesh varies with position and. Figure 3 shows that while the electric ﬁeld at the anode changes rapidly early in the calculation. The time-dependent solution and the Gouy–Chapman solution are computed on the same mesh. showing the convergence to the Gouy–Chapman solution (shown by the circles). The correlation coefﬁcient as a function of the relaxation time The best way to evaluate how closely one curve ﬁts to a second curve is to evaluate the correlation coefﬁcient [20]. The potential is applied to the anode with an amplitude of 100 mV.1 1. have been ﬁtted with a . The time elapsed for each curve in microseconds is shown in the ﬁgure.0 M.98. where r = 1 for a perfect correlation. rather than the electric ﬁeld. φj .01. If the calculation is continued long enough (∼50 µs) the time-dependent case relaxes to be arbitrarily close to the Gouy– Chapman solution.0 µs 1. 101 mesh points are placed over a gap of 1 µm between electrodes. 60 5. Distribution of ρNa (−+−+−+) and ρCl (. 1. 10 27 50. r. unless otherwise stated.R Morrow et al 4. from the potentials out to a distance of 5λD from the electrode. τ . the mesh expands exponentially from one electrode to the centre of the solution and then contracts exponentially to the other electrode.0 µm. coefﬁcient is calculated using the potentials. τ .9988 and after 50 µs r = 0.2..001 to 1. (Note that.001–1.03 × 10−9 m2 s−1 . We deﬁne the relaxation time τ to be the time for the correlation factor to reach r = 0.01 M saline solution. The correlation 940 40 Gouy-Chapman Equation Relaxed Time-Dependent Solution after 50 µs 3 E (MVm-1) 30 1 0.3 20 0.-) at t = 0. Results 50 5. and the corresponding relaxation times.

43 exp(92V 2 ) µs.01 M and vary the voltage applied. The ﬁeld rises to its maximum value of 18 MV m−1 over the ﬁrst few microseconds and is maintained at this value until the end of the pulse when it falls just as rapidly back to zero. When we keep the molarity constant at 0. In order to calculate an actual external circuit current using equation (12). we obtain the empirical equation τ ≈ 1. The results presented above are dependent on the voltage across the gap which has so far been kept constant.5 0.2 0.03 nm from the surface of the anode is shown in ﬁgure 6.01 M the Debye length is λD = 3.8 1. for the realistic voltage waveform used the displacement current is negligible.6 1 1. curve deﬁned by τ = 0.-) computed using equation (12) and the displacement current (· · · · · ·).5 0 5 Time (µs) 15 20 X (nm) Figure 3.3 Relaxed Time-Dependent Solution after 50 µs Gouy-Chapman Equation 1.517 µs. In order to display relative contributions of the conduction and displacement currents the ﬁrst 1 µs of the data for ﬁgure 4 is shown in ﬁgure 5. Note that from equation (12) any change in the area of the electrodes does not change the ratio of the conduction current to the displacement current.0 1. For example. (16) When equations (15) and (16) are combined we obtain the following more general empirical equation with both the effects of molarity and voltage included: τ ≈ 0.517 exp(92V 2 ) µs. except at the higher voltages and lowest molarity of 0. The rise and fall times for the voltage impulse were 0.128M −0. the current and voltage waveforms shown in ﬁgure 4 are obtained. is displayed for 20 µs and is plotted on the same graph as the current (. For a saline concentration of 0. (17) The accuracy of equation (17) over the range of parameters of interest can best be illustrated in tabular form as shown in table 1.5 0. the effect of a voltage impulse on a 0. the electrodes have been assumed to be 1 cm in diameter. This consistency is due to the fact that the data used closely obey the Nernst-Townsend formula [21] applied to liquids as Nernst ﬁrst envisioned for electrolytic ions in 1889: D kT = .0 0 0 5 10 15 20 25 30 –1. When a square-wave voltage impulse of amplitude 100 mV is applied to the 1 µm gap ﬁlled with a 0. Figure 4.05 E (MVm-1) 1 0 0.4 Potential X 10 (V).4 3. (15) Equation (15) ﬁts the data quite well and is similar to equation (11) for the Debye length which can be written as [4] λD = 0. The voltage waveform (——) computed using equation (14).04 nm. the time evolution (over a period of 20 µs) of the electric ﬁeld 0.321M −0. 6. 5. showing a similarly brief ﬁeld reversal to a peak of −0. The ﬁt is generally within ∼10%. the pulse width was 10 µs and the pulse voltage as a function of time was computed using equation (14).09 MV m−1 at the end of the impulse. These time-dependent solutions allow us to determine the time history of the electric ﬁeld in different parts of the solution in order to predict the effects these ﬁelds may have on proteins in those regions.3.001 M which is probably too low for most experiments with proteins. Discussion Such close agreement between the relaxed time-dependent solution and the Gouy–Chapman solution is remarkable.0 –1 0.6 –0. The time elapsed since the application of the +100 mV bias for each curve in microseconds is shown in the ﬁgure.. also shown in ﬁgure 6 for the same period. V . Clearly.304M −0.5 1. It remains at zero for the rest of the impulse. (18) µ e 941 . attains its maximum value of 0..01 M saline solution between two insulated electrodes 1 µm apart was studied. Current (A) 0. The development of the electric ﬁeld distribution near the electrode and in the bulk solution showing the convergence to the Gouy–Chapman solution (◦).2 0.09 MV m−1 in the ﬁrst microsecond and decays back to zero after the second microsecond.8 0.01 0.01 M solution. In contrast.5 nm. An example of the use of the time-dependent method To illustrate the application of our time-dependent method. This geometry includes the double-layers at both the cathode and the anode.1 µs. the time evolution of the electric ﬁeld at the centre of the saline solution.Development of electric double-layers 2 1. particularly since no adjustment has been made to the physical data to bring this about. indicating that τ ∝ λD .

06 3. The results for the correlation coefﬁcient are even more remarkable since calculations continued for 50 µs resulted in r = 0.001–1. (Note that a very abrupt voltage rise would lead to a very large displacement current spike.. The direct proportionality of the relaxation time to the Debye length for a ﬁxed applied voltage. The time τR . is because the ions have to move further to create a larger double-layer when the Debye length is large at low molarity. Consequently. The voltage waveform (——) computed using equation (14). for 20 µs after the start of the voltage impulse.57 11.4 0. Note that this result contrasts with the small perturbation results of Hunter and O’Brien et al who ﬁnd the time scale proportional to the square of the Debye length. with a negligible contribution from the displacement current.0 τR 1.98 compared with τ from equation (17).32 23.13 0.0 M) and voltages (10–175 mV) of interest. Equation (17) should prove useful for making estimates of double-layer formation times in many situations involving the application of bias voltage to solutions containing charged particles. The empirical equation (17) derived from the results estimates the double-layer formation time to within ∼10% over most of the range of molarities (0.) When the voltage goes back to zero the ions must relax back to their original positions. The current effectively stops ﬂowing at ∼4 µs. This is because more ions must move to produce a double-layer with the same Debye length to screen the larger potential. in microseconds.3 0.R Morrow et al Table 1. Molarity 1. and there is a reverse current pulse with a similar relaxation time (ﬁgure 4).43 3.2 109 0.32 1. this corresponds well with the relaxation time of ∼3. as well as the time duration of the circuit current (ﬁgure 4). since the solution relaxes to the generally accepted Gouy–Chapman results. The shape of the double-layer remains the same as the applied voltage is increased resulting in a higher electric ﬁeld at the electrode due to the increased potential gradient at higher applied voltage.5 µs for a correlation coefﬁcient r = 0.-) computed using equation (12) and the displacement current (· · · · · ·). Note that Ec has been multiplied by a factor of 100 in order to directly compare its waveform with that for Es .1 τ 0. The start of the current and voltage waveforms showing the magnitude of the displacement current.17 6.9 τR 4.42 1.49 3. The relaxation time. gives a good measure of the time taken for the system to reach the steady state.0 76 1 0. For a ﬁxed molarity the relaxation time increases exponentially with the square of the applied voltage.02 25.2 0. This result can be attributed in part to the accuracy of the ﬂux-corrected transport algorithm used to solve the continuity equations.5 0.33 7.40 36. 942 The excellent agreement found between the timedependent solution and the Gouy–Chapman equation means that the time-dependent solutions can be used for any distance and potential values.8 0.2 0 0.98.59 11.14 0. Es .2 0 –0.1 0.6 0.74 11.03 nm from the anode. Also.92 τ 0.4 0.39 44.14 τR 0.8 0. more time is taken to form the double-layer as more ions must move towards or away from the electrode in order to generate this higher electric ﬁeld. when the molarity of the saline solution is changed. at the centre of the saline solution 0.93 1.46 1.9 1 Time (µs) Figure 5. As the voltage rises in the calculation so does the current due to ion motion (ﬁgure 4)..45 11.01 τ 1.999 98.4 0. The practical example of a square-wave voltage applied to a 1 µm thick saline solution shows how the method can be applied to obtain results not readily available by other means.06 3. 20 15 Es 10 5 0 –5 Ec X 100 –10 0 5 10 15 20 Time (µs) Figure 6. for the time-dependent solution to relax to r = 0.5 µm from the anode and cathode.8 0. Development of the electric ﬁeld 0. the results at times before total relaxation is achieved can be expected to be accurate. exceeding the accuracy of the input data. In the double-layer near the anode the electric ﬁeld (ﬁgure 5) rises with the same time constant as the relaxation E (MVm-1) Potential X 10 (V).98. is displayed for 20 µs and is plotted on the same graph as the current (.0 Voltage (mV) 10 100 150 175 τR 0.6 0.001 τ 4. deﬁned as the time at which the correlation factor has risen to 0. and of the electric ﬁeld.01 2.32 0. Ec .7 0. Current (A) .

the current reverses and the ions move back to their original positions. 35 L69 [16] Roache R P 1972 Computational Fluid Dynamics (Albuquerque: Hermosa) [17] Abramowitz M and Stegun I A (ed) 1972 Handbook of Mathematical Functions with Formulas. Phys. D: Appl.6% of the gap. 2 74 1607 [7] O’Brien R W 1986 J. Phys. Tony Murphy and George Georghiou for their help in reviewing the article. 105 6507 [3] Butt H-J. Comput. The authors acknowledge the award of an Australian Research Council Discovery Grant to support this work. References [1] Honig B and Nicholls A 1995 Science 268 1144 [2] Rocchia W. John Lowke. rising sharply as the voltage is applied. Alexov E. At the centre of the saline solution the behaviour of the electric ﬁeld is quite different (ﬁgure 6). Phys. 30 3099 [14] Morrow R and Lowke J J 1997 J. Faraday Trans. Thus.: Condens. and Honig B 2001 J. Phys. Phys. Conclusions Such excellent agreement achieved between the timedependent solutions in the steady state and the solution of the Gouy–Chapman equation gives considerable conﬁdence in the methods used to obtain the time-dependent solutions. D: Appl. Phys. The electric ﬁeld then decays with the characteristic time constant as the double-layers form at the electrodes and the current decays. 80 61 [13] Morrow R 1997 J. (CTAC 91) ed J Noye (Singapore: World Scientiﬁc) p 347 [12] Steinle P and Morrow R 1989 J. 943 . 30 614 [15] Morrow R and Blackburn T R 2002 J. 190 71–86 [9] Tankovsky N and Syrakov E 2005 J. Acknowledgments The authors thank Drs Vivienne Bowers-Morrow. When the applied voltage goes to zero. relaxing back to zero with a similar time constant as the ions relax back to their original positions. Chem. the ions in the double-layers provide exactly the reverse ﬁeld needed to reverse the ion ﬂow back to the original state. Phys. We acknowledge many useful discussions with Alexandr and thank Peter Andrews for his encyclopaedic knowledge and inﬁnite patience. Graphs and Mathematical Tables (New York: Wiley) [18] Atkins P W 1998 Physical Chemistry (Oxford: Oxford University Press) p 948 [19] Adamson A W 1973 A Textbook of Physical Chemistry (New York: Academic) [20] Spiegel M R and Stephens L J 1999 Schaum’s Outline of Theory and Problems of Statistics 3rd edn (New York: McGraw-Hill) [21] Huxley L G H and Crompton R W 1974 The Diffusion and Drift of Electrons in Gases (New York: Wiley) 7. The time-dependent solution is not restricted by any of the limitations which apply to the linear Poisson–Boltzmann equation. When the applied voltage goes to zero. 32 L20 [11] Morrow R and Noye J 1989 Computational Techniques and Applications Conf. D: Appl. This is to be expected as the doublelayers only occupy ∼0. Phys. Fluid Mech.Development of electric double-layers time as the current and stays high while the voltage is on. Graf K and Kappl M 2003 Physics and Chemistry of Interfaces (Weinheim: Wiley-VCH) [4] Israelachvili J N 1985 Intermolecular and Surface Forces (London: Academic) [5] Hunter R J 2001 Foundations of Colloid Science (Oxford: Oxford University Press) [6] O’Brien R W and White L R 1978 J. The empirical equations derived for estimating the relaxation time for the formation of the double-layer should prove useful approximate guides for estimating the formation times for double-layers for a wide range of solution concentrations and applied voltages. Chem. D: Appl. the ions in the body of the gap supply most of the current. Matter 17 1225–38 [10] Morrow R and Sato N 1999 J. while the build up of ions at the electrodes creates a reverse ﬁeld that stops the ﬂow. the charges built up at the electrodes cause the ﬁeld to reverse at the centre of the saline solution. Colloid Interface Sci. This indicates that the intermediate solutions before the steady state is reached should also be reliable. 113 81 [8] O’Brien R W 1988 J. Phys. Soc. It is clear from the similarities of the current waveforms (ﬁgure 4) and the electric ﬁeld at the centre of the saline solution (ﬁgure 6) that the current is mainly due to ions moving in the body of the solution. The practical example shows how the development of the electric ﬁelds at different times and positions during a voltage pulse can be examined in detail in order to determine how proteins or other macromolecules in solution can be manipulated by the application of electric potentials. Phys. Phys.

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