918 resultados para Air electric potential gradient


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Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes.

Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H3O+(g), can protonate most (non-alkane) organic species, whereas H3O+(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the ‘function’ of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (< 1 nm thick) is an arduous task. While recent advances in surface-specific spectroscopies have provided valuable information regarding the structure of aqueous interfaces, but structure alone is inadequate to decipher the function. By similar analogy, theoretical predictions based on classical molecular dynamics have remained limited in their scope.

Recently, we have adapted an analytical electrospray ionization mass spectrometer (ESIMS) for probing reactions at the gas-liquid interface in real time. This technique is direct, surface-specific,and provides unambiguous mass-to-charge ratios of interfacial species. With this innovation, we have been able to investigate the following:

1. How do anions mediate proton transfers at the air-water interface?

2. What is the basis for the negative surface potential at the air-water interface?

3. What is the mechanism for catalysis ‘on-water’?

In addition to our experiments with the ESIMS, we applied quantum mechanics and molecular dynamics to simulate our experiments toward gaining insight at the molecular scale. Our results unambiguously demonstrated the role of electrostatic-reorganization of interfacial water during proton transfer events. With our experimental and theoretical results on the ‘superacidity’ of the surface of mildly acidic water, we also explored implications on atmospheric chemistry and green chemistry. Our most recent results explained the basis for the negative charge of the air-water interface and showed that the water-hydrophobe interface could serve as a site for enhanced autodissociation of water compared to the condensed phase.

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A novel technique of controlling the evolution of the filamentation was experimentally demonstrated in an argon gas-filled tube. The entrance of the filament was heated by a furnace and the other end was cooled with air, which resulted in the temperature gradient distribution along the tube. The experimental results show that multiple filaments are merged into a single filament and then no filament by only increasing the temperature at the entrance of the filament. Also, the filament can appear and disappear after increasing the local temperature and input pulse energy in turn. This technique offers another degree of freedom to control the filamentation and opens a new way for multi-mJ level monocycle pulse generation through filamentation in the noble gas.

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Part I

Regression analyses are performed on in vivo hemodialysis data for the transfer of creatinine, urea, uric acid and inorganic phosphate to determine the effects of variations in certain parameters on the efficiency of dialysis with a Kiil dialyzer. In calculating the mass transfer rates across the membrane, the effects of cell-plasma mass transfer kinetics are considered. The concept of the effective permeability coefficient for the red cell membrane is introduced to account for these effects. A discussion of the consequences of neglecting cell-plasma kinetics, as has been done to date in the literature, is presented.

A physical model for the Kiil dialyzer is presented in order to calculate the available membrane area for mass transfer, the linear blood and dialysate velocities, and other variables. The equations used to determine the independent variables of the regression analyses are presented. The potential dependent variables in the analyses are discussed.

Regression analyses were carried out considering overall mass-transfer coefficients, dialysances, relative dialysances, and relative permeabilities for each substance as the dependent variables. The independent variables were linear blood velocity, linear dialysate velocity, the pressure difference across the membrane, the elapsed time of dialysis, the blood hematocrit, and the arterial plasma concentrations of each substance transferred. The resulting correlations are tabulated, presented graphically, and discussed. The implications of these correlations are discussed from the viewpoint of a research investigator and from the viewpoint of patient treatment.

Recommendations for further experimental work are presented.

Part II

The interfacial structure of concurrent air-water flow in a two-inch diameter horizontal tube in the wavy flow regime has been measured using resistance wave gages. The median water depth, r.m.s. wave height, wave frequency, extrema frequency, and wave velocity have been measured as functions of air and water flow rates. Reynolds numbers, Froude numbers, Weber numbers, and bulk velocities for each phase may be calculated from these measurements. No theory for wave formation and propagation available in the literature was sufficient to describe these results.

The water surface level distribution generally is not adequately represented as a stationary Gaussian process. Five types of deviation from the Gaussian process function were noted in this work. The presence of the tube walls and the relatively large interfacial shear stresses precludes the use of simple statistical analyses to describe the interfacial structure. A detailed study of the behavior of individual fluid elements near the interface may be necessary to describe adequately wavy two-phase flow in systems similar to the one used in this work.

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The current power grid is on the cusp of modernization due to the emergence of distributed generation and controllable loads, as well as renewable energy. On one hand, distributed and renewable generation is volatile and difficult to dispatch. On the other hand, controllable loads provide significant potential for compensating for the uncertainties. In a future grid where there are thousands or millions of controllable loads and a large portion of the generation comes from volatile sources like wind and solar, distributed control that shifts or reduces the power consumption of electric loads in a reliable and economic way would be highly valuable.

Load control needs to be conducted with network awareness. Otherwise, voltage violations and overloading of circuit devices are likely. To model these effects, network power flows and voltages have to be considered explicitly. However, the physical laws that determine power flows and voltages are nonlinear. Furthermore, while distributed generation and controllable loads are mostly located in distribution networks that are multiphase and radial, most of the power flow studies focus on single-phase networks.

This thesis focuses on distributed load control in multiphase radial distribution networks. In particular, we first study distributed load control without considering network constraints, and then consider network-aware distributed load control.

Distributed implementation of load control is the main challenge if network constraints can be ignored. In this case, we first ignore the uncertainties in renewable generation and load arrivals, and propose a distributed load control algorithm, Algorithm 1, that optimally schedules the deferrable loads to shape the net electricity demand. Deferrable loads refer to loads whose total energy consumption is fixed, but energy usage can be shifted over time in response to network conditions. Algorithm 1 is a distributed gradient decent algorithm, and empirically converges to optimal deferrable load schedules within 15 iterations.

We then extend Algorithm 1 to a real-time setup where deferrable loads arrive over time, and only imprecise predictions about future renewable generation and load are available at the time of decision making. The real-time algorithm Algorithm 2 is based on model-predictive control: Algorithm 2 uses updated predictions on renewable generation as the true values, and computes a pseudo load to simulate future deferrable load. The pseudo load consumes 0 power at the current time step, and its total energy consumption equals the expectation of future deferrable load total energy request.

Network constraints, e.g., transformer loading constraints and voltage regulation constraints, bring significant challenge to the load control problem since power flows and voltages are governed by nonlinear physical laws. Remarkably, distribution networks are usually multiphase and radial. Two approaches are explored to overcome this challenge: one based on convex relaxation and the other that seeks a locally optimal load schedule.

To explore the convex relaxation approach, a novel but equivalent power flow model, the branch flow model, is developed, and a semidefinite programming relaxation, called BFM-SDP, is obtained using the branch flow model. BFM-SDP is mathematically equivalent to a standard convex relaxation proposed in the literature, but numerically is much more stable. Empirical studies show that BFM-SDP is numerically exact for the IEEE 13-, 34-, 37-, 123-bus networks and a real-world 2065-bus network, while the standard convex relaxation is numerically exact for only two of these networks.

Theoretical guarantees on the exactness of convex relaxations are provided for two types of networks: single-phase radial alternative-current (AC) networks, and single-phase mesh direct-current (DC) networks. In particular, for single-phase radial AC networks, we prove that a second-order cone program (SOCP) relaxation is exact if voltage upper bounds are not binding; we also modify the optimal load control problem so that its SOCP relaxation is always exact. For single-phase mesh DC networks, we prove that an SOCP relaxation is exact if 1) voltage upper bounds are not binding, or 2) voltage upper bounds are uniform and power injection lower bounds are strictly negative; we also modify the optimal load control problem so that its SOCP relaxation is always exact.

To seek a locally optimal load schedule, a distributed gradient-decent algorithm, Algorithm 9, is proposed. The suboptimality gap of the algorithm is rigorously characterized and close to 0 for practical networks. Furthermore, unlike the convex relaxation approach, Algorithm 9 ensures a feasible solution. The gradients used in Algorithm 9 are estimated based on a linear approximation of the power flow, which is derived with the following assumptions: 1) line losses are negligible; and 2) voltages are reasonably balanced. Both assumptions are satisfied in practical distribution networks. Empirical results show that Algorithm 9 obtains 70+ times speed up over the convex relaxation approach, at the cost of a suboptimality within numerical precision.

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Part I

The electric birefringence of dilute DNA solutions has been studied in considerable detail and on a large number of samples, but no new and reliable information was discovered concerning the tertiary structure of DNA. The large number of variables which effect the birefringence results is discussed and suggestions are made for further work on the subject.

The DNA molecules have been aligned in a rapidly alternating (10 to 20 kc/sec) square wave field confirming that the orientation mechanism is that of counterion polarization. A simple empirical relation between the steady state birefringence, Δnst, and the square of the electric field, E, has been found: Δnst = E2/(a E2 + b), where a = 1/Δns and b = (E2/Δnst)E→o. Δns is the birefringence extrapolated to infinite field strength.

The molecules show a distribution of relaxation times from 10-4 to 0.2 sec, which is consistent with expectations for flexible coil molecules. The birefringence and the relaxation times decrease with increasing salt concentrations. They also depend on the field strength and pulse duration in a rather non-reproducible manner, which may be due in part to changes in the composition of the solution or in the molecular structure of the DNA (other than denaturation). Further progress depends on the development of some control over these effects.

Part II

The specificity of the dissociation of reconstituted and native deoxyribonucleohistones (DNH) by monovalent salt solutions has been investigated. A novel zone ultracentrifugation method is used in which the DNH is sedimented as a zone through a preformed salt gradient, superimposed on a stabilizing D2O (sucrose) density gradient. The results, obtained by scanning the quartz sedimentation tubes in a spectrophotometer, were verified by the conventional, preparative sedimentation technique. Procedures are discussed for the detection of microgram quantities of histones, since low concentrations must be used to prevent excessive aggregation of the DNH.

The data show that major histone fractions are selectively dissociated from DNH by increasing salt concentrations: Lysine rich histone (H I) dissociates gradually between 0.1 and 0.3 F, slightly lysine rich histone (H II) dissociates as a narrow band between 0.35 and 0.5 F, and arginine rich histone (H III, H IV) dissociates gradually above 0.5 F NaClO4.

The activity of the partially dissociated, native DNH in sustaining RNA synthesis, their mobility and their unusual heat denaturation and renaturation behavior are described. The two-step melting behavior of the material indicates that the histones are non-randomly distributed along the DNA, but the implications are that the uncovered regions are not of gene-size length.

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Part 1. Many interesting visual and mechanical phenomena occur in the critical region of fluids, both for the gas-liquid and liquid-liquid transitions. The precise thermodynamic and transport behavior here has some broad consequences for the molecular theory of liquids. Previous studies in this laboratory on a liquid-liquid critical mixture via ultrasonics supported a basically classical analysis of fluid behavior by M. Fixman (e. g., the free energy is assumed analytic in intensive variables in the thermodynamics)--at least when the fluid is not too close to critical. A breakdown in classical concepts is evidenced close to critical, in some well-defined ways. We have studied herein a liquid-liquid critical system of complementary nature (possessing a lower critical mixing or consolute temperature) to all previous mixtures, to look for new qualitative critical behavior. We did not find such new behavior in the ultrasonic absorption ascribable to the critical fluctuations, but we did find extra absorption due to chemical processes (yet these are related to the mixing behavior generating the lower consolute point). We rederived, corrected, and extended Fixman's analysis to interpret our experimental results in these more complex circumstances. The entire account of theory and experiment is prefaced by an extensive introduction recounting the general status of liquid state theory. The introduction provides a context for our present work, and also points out problems deserving attention. Interest in these problems was stimulated by this work but also by work in Part 3.

Part 2. Among variational theories of electronic structure, the Hartree-Fock theory has proved particularly valuable for a practical understanding of such properties as chemical binding, electric multipole moments, and X-ray scattering intensity. It also provides the most tractable method of calculating first-order properties under external or internal one-electron perturbations, either developed explicitly in orders of perturbation theory or in the fully self-consistent method. The accuracy and consistency of first-order properties are poorer than those of zero-order properties, but this is most often due to the use of explicit approximations in solving the perturbed equations, or to inadequacy of the variational basis in size or composition. We have calculated the electric polarizabilities of H2, He, Li, Be, LiH, and N2 by Hartree-Fock theory, using exact perturbation theory or the fully self-consistent method, as dictated by convenience. By careful studies on total basis set composition, we obtained good approximations to limiting Hartree-Fock values of polarizabilities with bases of reasonable size. The values for all species, and for each direction in the molecular cases, are within 8% of experiment, or of best theoretical values in the absence of the former. Our results support the use of unadorned Hartree-Pock theory for static polarizabilities needed in interpreting electron-molecule scattering data, collision-induced light scattering experiments, and other phenomena involving experimentally inaccessible polarizabilities.

Part 3. Numerical integration of the close-coupled scattering equations has been carried out to obtain vibrational transition probabilities for some models of the electronically adiabatic H2-H2 collision. All the models use a Lennard-Jones interaction potential between nearest atoms in the collision partners. We have analyzed the results for some insight into the vibrational excitation process in its dependence on the energy of collision, the nature of the vibrational binding potential, and other factors. We conclude also that replacement of earlier, simpler models of the interaction potential by the Lennard-Jones form adds very little realism for all the complication it introduces. A brief introduction precedes the presentation of our work and places it in the context of attempts to understand the collisional activation process in chemical reactions as well as some other chemical dynamics.

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YAlO3 single crystal doped with Ce3+ at concentration 1% was grown by the temperature gradient technique. The as-grown crystal was pink. After H-2 annealing or air annealing at 1400degreesC for 20 h, the crystal was turned into colorless. We concluded there were two kinds of color centers in the as-grown crystal. One is F+ center attributed to absorption band peaking at about 530 nm, the other is O- center attributed to absorption band peaking at about 390 nm. This color centers model can be applied in explaining the experiment phenomena including the color changes, the absorption spectra changes, and the light yield changes of Ce:YAP crystals before and after annealing. (C) 2004 American Institute of Physics.

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A ssur ing the v itality and survival potential of live-caught Atlantic cod (Gadus morhua) is important for improving the sorting of fish before net penning operations designed to hold fish for growth and later market. When Atlantic cod are captured by Danish seine, the most commonly used fishing gear for live-caught fish, they undergo stressors such as forced swimming, net abrasion, and air exposure. Laboratory experiments (at an air temperature of 9°C and water temperature of 8°C) were conducted with the aim of constructing a RAMP (reflex action mortality predictor) curve for prediction of vitality and survival potential in Atlantic cod captured in Danish seines, by varying the levels of these stressors. Atlantic cod exposed to increased duration in air (5–20 min) showed increased reflex impairment and mortality, with 75% mortality at 10 minutes of air exposure. Forced swimming in combination with net abrasion and air exposure did not increase reflex impairment or mortality above that associated with air exposure alone. The Atlantic cod RAMP curves indicated that fish with reflex impairment less than 50% would not show mortality and would likely recover from capture stress.

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The potential adverse human health and climate impacts of emissions from UK airports have become a significant political issue, yet the emissions, air quality impacts and health impacts attributable to UK airports remain largely unstudied. We produce an inventory of UK airport emissions - including aircraft landing and takeoff (LTO) operations and airside support equipment - with uncertainties quantified. The airports studied account for more than 95% of UK air passengers in 2005. We estimate that in 2005, UK airports emitted 10.2 Gg [-23 to +29%] of NOx, 0.73 Gg [-29 to +32%] of SO2, 11.7 Gg [-42 to +77%] of CO, 1.8 Gg [-59 to +155%] of HC, 2.4 Tg [-13 to +12%] of CO2, and 0.31 Gg [-36 to +45%] of PM2.5. This translates to 2.5 Tg [-12 to +12%] CO2-eq using Global Warming Potentials for a 100-year time horizon. Uncertainty estimates were based on analysis of data from aircraft emissions measurement campaigns and analyses of aircraft operations.The First-Order Approximation (FOA3) - currently the standard approach used to estimate particulate matter emissions from aircraft - is compared to measurements and it is shown that there are discrepancies greater than an order of magnitude for 40% of cases for both organic carbon and black carbon emissions indices. Modified methods to approximate organic carbon emissions, arising from incomplete combustion and lubrication oil, and black carbon are proposed. These alterations lead to factor 8 and a 44% increase in the annual emissions estimates of black and organic carbon particulate matter, respectively, leading to a factor 3.4 increase in total PM2.5 emissions compared to the current FOA3 methodology. Our estimates of emissions are used in Part II to quantify the air quality and health impacts of UK airports, to assess mitigation options, and to estimate the impacts of a potential London airport expansion. © 2011 Elsevier Ltd.

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The effects of stratification on a series of highly swirling turbulent flames under globally lean conditions (φg=0.75) are investigated using a new high-spatial resolution multi-scalar dataset. This dataset features two key properties: high spatial resolution which approaches the 60 micron optical limit of the measurement system, and a wavelet oversampling methodology which significantly reduces the influence of noise. Furthermore, the very large number of realizations (30,000) acquired in the stratified cases permits statistically significant results to be obtained even after aggressive conditioning is applied. Data are doubly conditioned on equivalence ratio and the degree of stratification across the flame in each instantaneous realization. The influence of stoichiometry is limited by conditioning on the equivalence ratio at the location of peak CO mass fraction, which is shown to be a good surrogate for the location of peak heat release rate, while the stratification is quantified using a linear gradient in equivalence ratio across the instantaneous flame front. This advanced conditioning enables robust comparisons with the baseline lean premixed flame. Species mass fractions of both carbon monoxide and hydrogen are increased in temperature space under stratified conditions. Stratification is also shown to significantly increase thermal gradients, yet the derived three-dimensional flame surface density is shown to be relatively insensitive to stratification. Whilst the presence of instantaneous stratification broadens the curvature distribution relative to the premixed case, the degree of broadening is not significantly influenced by the range of global stratification ratios examined in this study. © 2012 The Combustion Institute.

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Abstract-Mathematical modelling techniques are used to predict the axisymmetric air flow pattern developed by a state-of-the-art Banged exhaust hood which is reinforced by a turbulent radial jet flow. The high Reynolds number modelling techniques adopted allow the complexity of determining the hood's air Bow to be reduced and provide a means of identifying and assessing the various parameters that control the air Bow. The mathematical model is formulated in terms of the Stokes steam function, ψ, and the governing equations of fluid motion are solved using finite-difference techniques. The injection flow of the exhaust hood is modelled as a turbulent radial jet and the entrained Bow is assumed to be an inviscid potential flow. Comparisons made between contours of constant air speed and centre-line air speeds deduced from the model and all the available experimental data show good agreement over a wide range of typical operating conditions. | Mathematical modelling techniques are used to predict the axisymmetric air flow pattern developed by a state-of-the-art flanged exhaust hood which is reinforced by a turbulent radial jet flow. The high Reynolds number modelling techniques adopted allow the complexity of determining the hood's air flow to be reduced and provide a means of identifying and assessing the various parameters that control the air flow. The mathematical model is formulated in terms of the Stokes steam function, Ψ, and the governing equations of fluid motion are solved using finite-difference techniques. The injection flow of the exhaust hood is modelled as a turbulent radial jet and the entrained flow is assumed to be an inviscid potential flow. Comparisons made between contours of constant air speed and centre-line air speeds deduced from the model and all the available experimental data show good agreement over a wide range of typical operating conditions.

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A key challenge in achieving good transient performance of highly boosted engines is the difficulty of accelerating the turbocharger from low air flow conditions (“turbo lag”). Multi-stage turbocharging, electric turbocharger assistance, electric compressors and hybrid powertrains are helpful in the mitigation of this deficit, but these technologies add significant cost and integration effort. Air-assist systems have the potential to be more cost-effective. Injecting compressed air into the intake manifold has received considerable attention, but the performance improvement offered by this concept is severely constrained by the compressor surge limit. The literature describes many schemes for generating the compressed gas, often involving significant mechanical complexity and/or cost. In this paper we demonstrate a novel exhaust assist system in which a reservoir is charged during braking. Experiments have been conducted using a 2.0 litre light-duty Diesel engine equipped with exhaust gas recirculation (EGR) and variable geometry turbine (VGT) coupled to an AC transient dynamometer, which was controlled to mimic engine load during in-gear braking and acceleration. The experimental results confirm that the proposed system reduces the time to torque during the 3rd gear tip-in by around 60%. Such a significant improvement was possible due to the increased acceleration of turbocharger immediately after the tip-in. Injecting the compressed gas into the exhaust manifold circumvents the problem of compressor surge and is the key enabler of the superior performance of the proposed concept.

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This paper studies 2G high-temperature superconducting (HTS) coils for electric machine armature windings, using finite element method (FEM) and H formulation. A FEM model for 2G HTS racetrack coil is built in COMSOL, and is well validated by comparing calculated ac loss with experimental measurements. The FEM model is used to calculate transport loss in HTS armature windings, using air-cored design. We find that distributed winding used in conventional machine design is an effective way to reduce transport loss of HTS armature winding, in terms of air-cored design. Based on our study, we give suggestions on the design of low loss HTS armature winding. © 2002-2011 IEEE.

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Flames propagating through a mixture with a gradient of equivalence ratio have been previously demonstrated to travel faster or slower than their equivalent premixed flames. The present study aims to numerically investigate the response of strained laminar methane-air flames to such gradients. The flames are simulated in a counterflow configuration where a premixed reactant stream at equivalence ratio φR opposes a hot equilibrium stream at equivalence ratio φP. Premixed and stratified flames are compared with respect to the equivalence ratio φ* and the corresponding gradient ∇φ* at the point of peak heat release rate, for three strain rates, a=50, 300 and 500s-1 and a range of φ*. The effect of different stratification levels is also investigated by varying the ratio of φP to φR, Θ. Results indicate that, as long as flames stabilize within the diffusion layer and Θ>1, increased heat release rate Q is seen throughout the progress variable space in comparison to the premixed state. In contrast, an attenuation of heat release rate is seen for Θ<1. The enhancement (or attenuation) of heat release varies monotonically with Θ. The effect of stratification on flame behavior becomes more pronounced as the strain rate increases. The present study reveals the mechanisms for the propagation of quasi-steady stratified flames under lean and rich conditions: stratified flames are primarily dominated by the diffusion of heat under lean conditions, and diffusion of H2 under rich conditions. Thanks to species and thermal support, stratified flames continue to burn beyond the premixed lean and rich flammability limits. Further investigation on the unsteady response of flames to the fluctuating equivalence ratio implies that the steady results represent the unsteady response well, as long as φ* and ∇φ* are similar in both steady and unsteady cases. © 2013 The Combustion Institute.

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A key challenge in achieving good transient performance of highly boosted engines is the difficulty of accelerating the turbocharger from low air flow conditions (turbo lag). Multi-stage turbocharging, electric turbocharger assistance, electric compressors and hybrid powertrains are helpful in the mitigation of this deficit, but these technologies add significant cost and integration effort. Air-assist systems have the potential to be more cost-effective. Injecting compressed air into the intake manifold has received considerable attention, but the performance improvement offered by this concept is severely constrained by the compressor surge limit. The literature describes many schemes for generating the compressed gas, often involving significant mechanical complexity and/or cost. In this paper we demonstrate a novel exhaust assist system in which a reservoir is charged during braking. Experiments have been conducted using a 2.0 litre light-duty Diesel engine equipped with exhaust gas recirculation (EGR) and variable geometry turbine (VGT) coupled to an AC transient dynamometer, which was controlled to mimic engine load during in-gear braking and acceleration. The experimental results confirm that the proposed system reduces the time to torque during the 3rd gear tip-in by around 60%. Such a significant improvement was possible due to the increased acceleration of turbocharger immediately after the tip-in. Injecting the compressed gas into the exhaust manifold circumvents the problem of compressor surge and is the key enabler of the superior performance of the proposed concept. Copyright © 2013 SAE International.