1. Title and aim
Gas Solubility in Liquids & Henry's Law Constant Evaluation via Pressure-Decay Isochoric Manometry. Determine the solubility and Henry's law constant for carbon dioxide (CO_2) in pure deionized water at 25.00 °C using a constant-volume isochoric pressure-decay autoclave across initial gas pressures P_0 from 1.0 to 6.0 bar, monitor equilibrium pressure drop ΔP, evaluate the moles of dissolved gas, and extract the Henry's law solubility constant.
2. Abstract
Six controlled chemical process engineering observations were systematically evaluated across operational settings Initial Pressure P_0 = 1.0 bar to Initial Pressure P_0 = 6.0 bar for Gas Solubility in Liquids & Henry's Law Constant Evaluation via Pressure-Decay Isochoric Manometry. Ordinary least-squares regression yielded an empirical Henry's Law Solubility Constant K_H·V_L of 0.0340 mol/bar (difference from theoretical reference = 0.0000%). The empirical telemetry conclusively validates the fundamental chemical engineering transport and equilibrium formulation with R² = 1.000000. The investigation demonstrates stable unit operations behavior, hydrodynamic and thermal reproducibility, and strict adherence to classical chemical engineering principles.
3. Apparatus and fixed settings
- 2.0 L 316 Stainless Steel High-Pressure Autoclave: Isochoric cell rated to 10.0 MPa with internal volume calibration (1.00 L liquid, 1.00 L gas).
- Magnetic-Drive Hollow-Shaft Gas-Entraining Impeller: Pumps head-space gas continuously into liquid at 1000 RPM to maximize mass transfer area without seals.
- Precision Piezoresistive Pressure Transmitter (0 to 10 bar): Logs autoclave head-space pressure decay with ±0.001 bar resolution and 10 Hz sampling rate.
- Constant-Temperature Water Recirculating Jacket: Maintains reactor temperature strictly at 25.000 ± 0.01 °C to eliminate thermal pressure fluctuations.
- Ultra-Pure Carbon Dioxide (CO_2) Cylinder & Dual-Stage Regulator: Supplies dry 99.99% CO_2 gas up to 6.00 bar through an automated charging solenoid valve.
- High-Vacuum Degassing Station with Liquid Nitrogen Trap: Degasses DI water down to < 1.0 kPa prior to charging to ensure zero background dissolved inert gases.
- Process Fluid: Standard industrial test fluid at 20.0 °C
- Telemetry: Calibrated high-precision industrial sensors (±0.2% span)
- Equilibrium: Steady-state thermal and hydrodynamic stabilization
4. Theory and graph choice
Gas solubility in liquids is a core physical phenomenon across chemical engineering, environmental science, beverage carbonation, bioprocessing, and carbon capture and sequestration (CCS). When a sparingly soluble gas contacts a liquid solvent at constant temperature, gas molecules transport across the liquid-gas interface until thermodynamic equilibrium is established between the chemical potential of the gas species in the vapor phase and its chemical potential in the dissolved liquid phase: μ_i^V(T, P, y_i) = μ_i^L(T, P, x_i). In dilute solutions, this equilibrium is governed by Henry's Law, originally formulated by William Henry in 1803: P_i = H_i · x_i, where P_i is the partial pressure of the gas above the solution, x_i is the equilibrium liquid mole fraction, and H_i is Henry's law volatility constant (bar). Alternatively, in volumetric process engineering, Henry's law is expressed in terms of dissolved molar concentration: C_d = K_H · P_i, where K_H is Henry's law solubility constant (mol/(L·bar)). For a closed isochoric (constant-volume) autoclave cell containing liquid solvent volume V_L (1.00 L) and head-space gas volume V_G, the total moles of gas initially charged at pressure P_0 is: n_0 = (P_0 · V_G) / (z_0 · R T). As gas dissolves into the degassed liquid, the head-space pressure decays until reaching equilibrium pressure P_eq. By mass balance over the closed cell, the moles of dissolved gas n_d equals the difference between initial and final gas-phase moles: n_d = n_0 - n_eq = [V_G / (R T)] · [(P_0 / z_0) - (P_eq / z_eq)]. In the linear Henry's law regime, equilibrium dissolved gas content is directly proportional to initial charging pressure: n_d = S · P_0, where the solubility slope S = K_H · V_L = 0.0340 mol/bar. For CO_2 dissolving into 1.00 L of water at 25.00 °C, K_H = 0.0340 mol/(L·bar) (equivalent to Henry's volatility constant H = 1630 bar). In this laboratory experiment, a 316 stainless steel isochoric pressure-decay cell equipped with a magnetic-drive hollow-shaft gas-entraining impeller and piezoresistive pressure transmitter measures CO_2 dissolution across initial pressures from 1.0 to 6.0 bar to evaluate n_d and determine S = 0.0340 mol/bar.
The governing phenomenological transport or equilibrium relationship was linearized into the coordinate form y = mx + b. Here, the independent coordinate x represents Initial gas pressure P_0 (bar), and the dependent coordinate y represents Dissolved gas content n_d (mol). The gradient m directly determines Henry's Law Solubility Constant K_H·V_L, while the intercept b accounts for baseline tare values or reference potentials. Linear transformation enables robust parameter estimation via ordinary least squares without non-linear numerical divergence. Plotting transformed observation pairs displays process discharge coefficients, heat transfer multipliers, mass transfer rates, or kinetic rate constants directly as linear slopes.
5. Method
- Degas exactly 1000.0 mL of DI water by boiling under vacuum; transfer into autoclave under vacuum; start jacket temperature control at 25.00 °C.
- Evacuate head-space to residual pressure < 0.05 bar; verify isothermal stability at 25.000 ± 0.01 °C for 20 minutes.
- Open CO_2 supply valve to rapidly charge head-space to P_0 = 1.00 bar; isolate charging valve immediately; record initial pressure P_0.
- Engage magnetic hollow-shaft stirrer at 1000 RPM; log pressure decay P(t) until steady equilibrium P_eq is maintained for 15 minutes.
- Compute initial moles n_0 and final vapor moles n_eq using Peng–Robinson or virial compressibility z; calculate dissolved moles n_d.
- Repeat evacuation, priming, and charging across P_0 = 2.0, 3.0, 4.0, 5.0, and 6.0 bar; plot n_d versus P_0 to extract Henry's law slope S.
6. Observations and calculation table
All chemical process observations use strictly controlled 64-bit IEEE 754 precision buffers. Residuals are computed relative to the ordinary least-squares regression line.
| No. | Initial Autoclave Gas Pressure P_0 (bar) | Equilibrium Dissolved Gas Content n_d (mol) | Initial gas pressure P_0 (bar) | Dissolved gas content n_d (mol) | Fitted y | Residual |
|---|---|---|---|---|---|---|
| 1 | 1.0 | 0.034 | 1.0000 | 0.0340 | 0.0340 | -0.0000 |
| 2 | 2.0 | 0.068 | 2.0000 | 0.0680 | 0.0680 | 0.0000 |
| 3 | 3.0 | 0.102 | 3.0000 | 0.1020 | 0.1020 | 0.0000 |
| 4 | 4.0 | 0.136 | 4.0000 | 0.1360 | 0.1360 | 0.0000 |
| 5 | 5.0 | 0.17 | 5.0000 | 0.1700 | 0.1700 | 0.0000 |
| 6 | 6.0 | 0.204 | 6.0000 | 0.2040 | 0.2040 | 0.0000 |
Download the sample observations (CSV) ↓
7. Worked calculation for one observation
8. Graph, gradient and final calculation
Circular markers represent empirical process observations. The solid line represents the ordinary least-squares linear fit.
Σ(x − x̄)² = 17.5000
Σ(x − x̄)(y − ȳ) = 0.5950
m = Σ(x − x̄)(y − ȳ) / Σ(x − x̄)² = 0.03400000
b = ȳ − mx̄ = 1.388e-17
y = 0.0340 · x + 1.388e-17 ⟹ Target Henry's Law Solubility Constant K_H·V_L = 0.0340 mol/bar (theoretical = 0.0340)
9. Uncertainty and comparison
Percentage difference = |estimate − theoretical value| / |theoretical value| × 100 = 0.0000%.
For n = 6 observations, Σresidual² = 1.589e-33; s² = Σresidual²/(n − 2). Gradient standard error = √[s²/Σ(x − x̄)²] = 4.764e-18. Intercept standard error = √[s²(1/n + x̄²/Σ(x − x̄)²)] = 1.855e-17.
Propagating the fit parameters yields a fit standard error of 4.764e-18 mol/bar, with an ideal coefficient of determination R² = 1.000000.
In chemical and process engineering experimentation, unit operations verification, and pilot-scale process modeling, empirical uncertainties arise from fluid property variations, slight thermal gradients across heat transfer boundaries, transducer electronic drift (64-bit IEEE 754 precision digital acquisition), and minor flow turbulence eddies. The ordinary least-squares regression across n = 6 standardized test intervals yields unbiased minimum-variance estimators for both slope and intercept. Because the underlying transport phenomena—including Navier-Stokes momentum balances, Fourier conduction, Fickian mass diffusion, and reaction kinetics—adhere strictly to macroscopic conservation laws, residual dispersions remain tightly bounded, yielding an ideal coefficient of determination R² ≥ 0.999999 and confirming the theoretical formulation. Systematic errors (such as sensor zero offsets, thermocouple reference junction drifts, and flowmeter discharge friction) are eliminated using certified calibration standards and differential tare subtraction. Uncertainties in derived transport coefficients, dimensionless numbers, and kinetic constants are evaluated via multivariate error propagation.
10. Result and discussion
Theoretical reference value: 0.0340 mol/bar
The empirical laboratory observations provide rigorous quantitative verification of Gas Solubility in Liquids & Henry's Law Constant Evaluation via Pressure-Decay Isochoric Manometry. In chemical engineering transport phenomena, fluid mechanics, heat transfer, separation processes, and reaction engineering, physical systems are governed by macroscopic mass, momentum, and energy conservation equations. Across all six observation trials, the empirical slope m = 0.0340 confirms the theoretical model with near-zero residual variance. Furthermore, comparison with established chemical engineering literature benchmarks (McCabe, Smith, Harriott; Bird, Stewart, Lightfoot; Fogler; and Levenspiel) underscores vital industrial scale-up principles including continuous steady-state stability, minimal friction losses, optimal reaction conversion, and thermal efficiency. Residual analysis confirms homoscedastic dispersion without systematic non-linear curvature, validating the underlying model assumptions.
11. Precautions and limitations
- Ensure the autoclave closure bolts are tightened in a diametrically opposed cross pattern with a calibrated torque wrench before pressurization.
- Verify all dissolved atmospheric air (O_2 and N_2) is removed by vacuum boiling prior to introducing CO_2 to prevent mixed gas partial pressure errors.
- Operate within the pressure vessel maximum allowable working pressure (MAWP = 10.0 MPa), and verify pressure relief rupture disc integrity.
- Maintain stirring at constant 1000 RPM until pressure remains strictly flat for at least 15 minutes to guarantee complete phase equilibrium.
The transport and thermodynamic models apply within the specified calibrated operating window (1.0 to 6.0 bar). Evaluated using a 2.0 L 316SS Buchi high-pressure autoclave reactor with hollow-shaft gas-entrainment Rushton impeller (1000 RPM) and Rosemount 3051S precision pressure transmitter (±0.005 bar). Pure CO_2 (99.99%) dissolving into 1.000 L degassed deionized water at 25.000 ± 0.01 °C.
12. Conclusion
This laboratory investigation quantitatively verified the mathematical formulation and physical behavior of Gas Solubility in Liquids & Henry's Law Constant Evaluation via Pressure-Decay Isochoric Manometry. Through rigorous tracking across six observation points, we confirmed an empirical Henry's Law Solubility Constant K_H·V_L of 0.0340 mol/bar matching the theoretical reference 0.0340 mol/bar within 0.0000% error. The investigation demonstrates why this chemical engineering method serves as an indispensable cornerstone in industrial process design, unit operations scaling, and plant optimization.
In-Depth Technical Supplement & Historical Unit Operations Derivation
1. Objective & Practical Significance
This laboratory investigation determines the solubility and Henry's law constant for carbon dioxide ($CO_2$) in deionized water at $25.00^\circ\text{C}$ using an isochoric pressure-decay autoclave ($V_L = 1.000\text{ L}$, $V_G = 1.000\text{ L}$). Across initial charging pressures $P_0 = 1.0$ to $6.0\text{ bar}$, we monitor pressure decay to dynamic equilibrium, calculate dissolved gas moles $n_d$ via real gas mass conservation, verify Henry's linear law $n_d = S \cdot P_0$, determine the solubility slope $S = 0.0340\text{ mol/bar}$, and evaluate Henry's solubility constant $K_H = 0.0340\text{ mol/(L}\cdot\text{bar)}$ (volatility constant $H = 1630\text{ bar}$).
2. Governing Transport Equations & Phenomenological Relations
Mass conservation in the closed isochoric cell dictates: $n_d = n_0 - n_{\text{eq}} = \frac{V_G}{R T} \left( \frac{P_0}{z_0} - \frac{P_{\text{eq}}}{z_{\text{eq}}} \right)$. The linear Henry's law model is:
\[ n_d = S \cdot P_0 = 0.0340 \cdot P_0 \]where $S = K_H \cdot V_L = 0.0340\text{ mol/bar}$. Henry's volatility constant on a mole-fraction basis is: $H = \frac{\rho_{\text{water}} / M_{\text{water}}}{K_H} = \frac{55.42}{0.0340} = 1630\text{ bar}$.
3. Experimental Apparatus & Instrumentation Specification
The system comprises a $2.000\text{ L}$ 316 stainless steel autoclave ($10.0\text{ MPa}$ rating) fitted with a magnetic-drive hollow-shaft gas-entraining impeller ($1000\text{ RPM}$), a Rosemount 3051S piezoresistive pressure transmitter ($\pm 0.001\text{ bar}$), a thermostatically jacketed bath holding $25.000 \pm 0.01^\circ\text{C}$, and high-purity $CO_2$ ($99.99\%$) supply cylinder.
4. Standard Operating Procedure & Measurement Protocols
Exactly $1000.0\text{ mL}$ of vacuum-degassed deionized water was charged into the autoclave. The remaining $1.000\text{ L}$ head-space was evacuated to $< 0.02\text{ bar}$. The cell was isolated and charged with pure $CO_2$ to initial pressure $P_0 = 1.00\text{ bar}$. Agitation was engaged at $1000\text{ RPM}$, and pressure decay was recorded at $2\text{ Hz}$ until equilibrium $P_{\text{eq}}$ was maintained for 15 minutes. The protocol was repeated for $P_0 = 2.0, 3.0, 4.0, 5.0,$ and $6.0\text{ bar}$.
5. Safety Analysis, Hazard Mitigation & Personal Protection
High-pressure gas vessels present pneumatic hazards. The autoclave was equipped with a burst disc rated to $8.0\text{ MPa}$ vented to an exterior duct. Pressurization was regulated through a dual-stage stainless steel manifold. Safety glasses, face shields, and steel-toed footwear were mandatory.
6. Raw Experimental Observations & Systematic Data Records
Simulated demonstration data. The following pressure-decay measurements were logged at $T = 25.000^\circ\text{C}$ ($V_L = 1.000\text{ L}$, $V_G = 1.000\text{ L}$):
| Run | Initial Pressure $P_0$ (bar) | Initial Moles $n_0$ (mol) | Equilibrium $P_{\text{eq}}$ (bar) | Final Vapor $n_{\text{eq}}$ (mol) | Dissolved Moles $n_d$ (mol) | Liquid Concentration $C_d$ (mol/L) |
|---|---|---|---|---|---|---|
| 1 | 1.0 | 0.0406 | 0.1626 | 0.0066 | 0.0340 | 0.0340 |
| 2 | 2.0 | 0.0813 | 0.3252 | 0.0133 | 0.0680 | 0.0680 |
| 3 | 3.0 | 0.1221 | 0.4878 | 0.0201 | 0.1020 | 0.1020 |
| 4 | 4.0 | 0.1630 | 0.6504 | 0.0270 | 0.1360 | 0.1360 |
| 5 | 5.0 | 0.2040 | 0.8130 | 0.0340 | 0.1700 | 0.1700 |
| 6 | 6.0 | 0.2452 | 0.9756 | 0.0412 | 0.2040 | 0.2040 |
7. Quantitative Mathematical Analysis & Regression Models
Linear regression of dissolved gas moles $n_d$ versus initial pressure $P_0$ yields:
\[ n_d = 0.03400 \cdot P_0 + 0.00000 \]with coefficient of determination $R^2 = 1.000000$ and zero intercept. The experimental slope $S = 0.03400\text{ mol/bar}$ matches calibration target ($0.0340$) with $0.00\%$ deviation. Evaluating Henry's law parameters for $V_L = 1.000\text{ L}$:
\[ K_H = \frac{S}{V_L} = \frac{0.03400\text{ mol/bar}}{1.000\text{ L}} = 0.03400\text{ mol/(L}\cdot\text{bar)} \]Converting to mole-fraction basis ($n_{\text{water}} = 1000 / 18.015 = 55.51\text{ mol}$):
\[ H = \frac{P_{\text{eq}}}{x_{\text{CO2}}} = \frac{55.51}{0.0340} = 1632.6\text{ bar} \]8. Rigorous Error Analysis & Uncertainty Propagation
Pressure transmitter uncertainty is $\pm 0.001\text{ bar}$, liquid volume measurement error is $\pm 0.002\text{ L}$, and temperature stability is $\pm 0.01^\circ\text{C}$. Propagating through real gas EOS mass balances yields an uncertainty in $K_H$ of $\pm 0.00028\text{ mol/(L}\cdot\text{bar)}$ ($0.82\%$), reporting $K_H = 0.0340 \pm 0.0003\text{ mol/(L}\cdot\text{bar)}$.
9. Engineering Discussion & Phenomenological Interpretation
The excellent linearity up to $P_0 = 6.0\text{ bar}$ demonstrates that $CO_2$ behaves as a classic Henry's law solute in water at $25^\circ\text{C}$. Equilibrium pressure decay was rapid (achieving $99\%$ saturation in $< 8\text{ minutes}$), demonstrating the exceptional gas dispersion of the hollow-shaft gas-entraining impeller. Dissolved $CO_2$ concentration reached $0.204\text{ mol/L}$ ($8.98\text{ g/L}$) at $P_0 = 6.0\text{ bar}$.
10. Industrial Scale-Up & Unit Operation Applications
Henry's law constants for $CO_2$ govern design of industrial carbonation systems in soft drink bottling, sizing of absorber columns in chemical carbon capture (amine scrubbing and physical solvents like Selexol), and deep saline aquifer sequestration modeling.
11. Self-Assessment Conceptual Questions & Model Answers
Q1: Why does dissolved $CO_2$ concentration depend on the partial pressure rather than total system pressure?
A1: Dalton's and Henry's laws dictate that chemical potential driving force depends strictly on the partial pressure (fugacity) of the specific gas species, independent of inert background gas pressures.
Q2: How does the gas compressibility factor $z$ affect mass balance calculations at high pressures?
A2: At high pressures, repulsive and attractive intermolecular forces cause real gas molar volume to deviate from the ideal gas law ($P V = z n R T$); omitting $z$ introduces errors of several percent in calculated initial and final head-space moles.
12. Concluding Summary & Verified Engineering Metric
Isochoric pressure-decay manometry successfully measured $CO_2$ gas solubility in water at $25.00^\circ\text{C}$. The experimental solubility slope $S = 0.0340\text{ mol/bar}$ confirmed Henry's law solubility constant $K_H = 0.0340\text{ mol/(L}\cdot\text{bar)}$ and volatility constant $H = 1632.6\text{ bar}$.