During the working of a galvanic cell and with the passage of time.
1) Spontaneity of the cell reaction decreases, `E_(cell)` decreases
2) Reaction quotient `Q` decreases, `E_(cell)` increases
3) Reaction quotient `Q` increases, `E_(cell)` decreases
4) At equilibrium, `Q=K_(eq),E_(cell)=0`

Options

A. Spontaneity of the cell reaction decreases, `E_(cell)` decreases
B. Reaction quotient `Q` decreases, `E_(cell)` increases
C. Reaction quotient `Q` increases, `E_(cell)` decreases
D. At equilibrium, `Q=K_(eq),E_(cell)=0`

Explanation

To solve the question regarding the behavior of a galvanic cell over time, we can analyze the four given statements step by step.

### Step 1: Understanding the Galvanic Cell
A galvanic cell generates electrical energy through spontaneous chemical reactions. The spontaneity of the reaction is related to the cell potential, denoted as \( E_{cell} \).

### Step 2: Analyzing the Statements
1. **Spontaneity of the cell reaction decreases, \( E_{cell} \) decreases**:
- The spontaneity of a reaction is related to the Gibbs free energy change (\( \Delta G \)). The relationship is given by:
\[ \Delta G = -nFE_{cell} \]
- If \( E_{cell} \) decreases, \( \Delta G \) becomes less negative, indicating a decrease in spontaneity. Thus, this statement is **correct**.

2. **Reaction quotient \( Q \) decreases, \( E_{cell} \) increases**:
- According to the Nernst equation:
\[ E_{cell} = E^{\circ}_{cell} - \frac{RT}{nF} \ln Q \]
- If \( Q \) decreases, the term \( -\frac{RT}{nF} \ln Q \) becomes less negative, leading to an increase in \( E_{cell} \). Therefore, this statement is **correct**.

3. **Reaction quotient \( Q \) increases, \( E_{cell} \) decreases**:
- From the Nernst equation, if \( Q \) increases, the term \( -\frac{RT}{nF} \ln Q \) becomes more negative, which results in a decrease in \( E_{cell} \). Thus, this statement is **correct**.

4. **At equilibrium, \( Q = K_{eq}, E_{cell} = 0 \)**:
- At equilibrium, the reaction has reached a state where the concentrations of reactants and products no longer change, and thus \( E_{cell} \) becomes zero. This is also a well-established fact in electrochemistry. Therefore, this statement is **correct**.

### Conclusion
All four statements are correct regarding the behavior of a galvanic cell over time.

### Summary of Correct Answers:
1. Correct
2. Correct
3. Correct
4. Correct