The role of charge in microdroplet redox chemistry is explored, focusing on the thermodynamic alterations that occur in charged water microdroplets compared to bulk phases. The study uses theoretical simulations to investigate the formation of reactive species such as hydroxyl and hydrogen radicals and solvated electrons in water droplets with increasing charge imbalance. Key findings include: 1. **Hydration Enthalpy Changes**: The hydration enthalpy of OH\(^-\) and H\(^+\) decreases significantly (by >50 kcal/mol) at charge levels around 20-50% of the Rayleigh limit, making electron transfer thermodynamically favorable. 2. **Vertical Ionization Energy (VIE) and Vertical Electron Affinity (VEA)**: The VIE of OH\(^-\) decreases with increasing charge, while the VEA of H\(^+\) increases, indicating that electron transfer becomes more favorable. 3. **Scaling Arguments**: The theoretical results are extended to the experimental microdroplet length scale through scaling arguments, showing that the observed changes in hydration enthalpy, VIE, and VEA are quantifiable at this scale. 4. **Relevance to Experimental Observations**: The findings explain the accelerated redox chemistry observed in microdroplets, particularly the production of hydrogen peroxide (H\(_2\)O\(_2\)), and suggest that similar mechanisms may apply to other redox reactions. 5. **Dielectric Effects**: The dielectric constant of water is significantly reduced in charged droplets due to the inability of water to screen out the field of like charges, leading to an apparent dielectric constant of nearly 1. 6. **Conclusion**: The work provides a thermodynamic explanation for the accelerated redox chemistry in microdroplets, highlighting the importance of charge imbalance in altering reaction thermodynamics. This research contributes to the understanding of the unique properties of charged microdroplets and their potential applications in various chemical processes.The role of charge in microdroplet redox chemistry is explored, focusing on the thermodynamic alterations that occur in charged water microdroplets compared to bulk phases. The study uses theoretical simulations to investigate the formation of reactive species such as hydroxyl and hydrogen radicals and solvated electrons in water droplets with increasing charge imbalance. Key findings include: 1. **Hydration Enthalpy Changes**: The hydration enthalpy of OH\(^-\) and H\(^+\) decreases significantly (by >50 kcal/mol) at charge levels around 20-50% of the Rayleigh limit, making electron transfer thermodynamically favorable. 2. **Vertical Ionization Energy (VIE) and Vertical Electron Affinity (VEA)**: The VIE of OH\(^-\) decreases with increasing charge, while the VEA of H\(^+\) increases, indicating that electron transfer becomes more favorable. 3. **Scaling Arguments**: The theoretical results are extended to the experimental microdroplet length scale through scaling arguments, showing that the observed changes in hydration enthalpy, VIE, and VEA are quantifiable at this scale. 4. **Relevance to Experimental Observations**: The findings explain the accelerated redox chemistry observed in microdroplets, particularly the production of hydrogen peroxide (H\(_2\)O\(_2\)), and suggest that similar mechanisms may apply to other redox reactions. 5. **Dielectric Effects**: The dielectric constant of water is significantly reduced in charged droplets due to the inability of water to screen out the field of like charges, leading to an apparent dielectric constant of nearly 1. 6. **Conclusion**: The work provides a thermodynamic explanation for the accelerated redox chemistry in microdroplets, highlighting the importance of charge imbalance in altering reaction thermodynamics. This research contributes to the understanding of the unique properties of charged microdroplets and their potential applications in various chemical processes.