When you open the serial monitor it resets the Arduino, which was already running and had output a "4". Ideally this first output would be flushed and not appear, but it shows up sometimes. Other times you just get garbage characters. It's a minor flaw in the monitor tool.
Try this instead and you will see it's only printing once:
void setup(){
Serial.begin(9600);
Serial.println("\nStarting the sketch...\n");
int a =2;
int b =2;
int c = a + b;
Serial.println(c);
}
void loop(){
}